Unit's Summary

The basic role of chemical engineer, to put it very simply, is to convert raw material into a useful product,
for example converting wood to paper or sugarcane to sugar cubes and many more such examples. A
process is any operation or a series of operations by which a given task is accomplished. For example,
crushing of sugarcane to extract juice will form a process, further concentrating the juice by heating it in a
vessel or heat-exchanger will constitute another process. This process of concentrating the juice can be
schematically represented as a block diagram as shown below:

This course is concerned with accounting for material and energy flowing (or fed) in and out of such
processes or combination of several such processes. Any process will be carried out in equipment or a
series of equipment like heat-exchangers, tank-type vessels, stirred tanks, reactors, crusher, extractor,
distillation column, etc. We will use the words process, equipment, and unit interchangeably to simply
mean that a material or energy enters and leaves a process. The material that enters a process is referred as
input or feed and that leaves is known as output or product. We represent the process as blocks in this
course and input and output by arrows in and out of the process, respectively. These input and output
streams are referred as process streams.

In the present unit, we discuss different ways to characterize process stream in relation to applying
material and energy balances. Specifically, we define variables like flow rates, densities, concentration,
mole and mass fractions, compositions etc all of which are primarily used for quantifying material flow in
and out of the process.

Density and specific volume

Density of a substance is mass per unit volume of that substance. It is denoted by ρ and can be expressed
in units as kg/m3, g/cm3, g/L, lb/ft3 etc. The specific volume is inverse of density and is denoted by v.
Similarly we can define molar density as number of moles per unit volume and specific molar volume as
inverse of molar density (denoted by 𝑉𝑉�). Densities of pure solids and liquids are almost independent of
pressure and vary relatively slightly with temperature. Densities of many pure substance, mixture, and
solution can be found in several standard texts for example Perry's Chemical Engineering Handbook.
Methods of estimating densities of gases (or specific volume) are discussed later in this course.

Specific gravity (SG) for a substance is defined as ratio of density of that substance to the density of a
reference material a specified condition.
SG = ρ/ρ ref

For liquids and solids, ρ ref = , ρ water(l) (4oC)= 1.00 g/cm3=1000 kg/m3=62.43 lb/ft3. For gases reference is
usually taken as density if air at some standard temperature and pressure (usually 25oC and 1 atm). To be
precise, the SG is expressed as: 0.65 20oC/4oC which implies that the SG of liquid at 20oC is 0.65 relative
to water (l) at 4oC.

Note: In petroleum industry, SG is occasionally reported in terms of oAPI, oBe (Baume), and oTw
(Twaddel). However, these terms are given here for the sake of information and we will not be using
these representations for SG.

Flow rate: could be given as mass flow rate (with dimensions as mass/time and units as kg/s, kg/h etc),
volumetric flow rate (with units as L/min, ft3/h, m3/s etc.), or molar flow rate (kmol/min etc.). Two
commonly used instruments for measuring flow rate are orifice meter and rotameter.

Mole: Amount of substance corresponding to a specified number which is Avogadro's number

(=6.023×1023). Thus, one mole of apples would correspond to 6.023×1023 apples. However, this is always
used in context of chemical species (1mole of C-atoms, 1 mole of CO 2 , 1 mole of N 2 , 1 mole of air etc.).
For a chemical species:

1mole of species  Avogadro's no. of molecules or atoms  mass in grams numerically equal to its
molecular weight (for molecular species or chemical compound) or atomic weight (for atomic species).

Thus,

1 mole of C -atoms  12 g of C; 1 mole of O 2  32 g of O 2 ; 1 mole of CO 2  44 g of CO 2 .

Accordingly:

Number of moles = mass of species/Molecular weight

For different systems of units:

1 g-mole or 1 mole = mass of species in grams numerically equal to its molecular weight

1 kmol = mass of species in kilograms numerically equal to its molecular weight

1 lb-mol = mass of species in lb numerically equal to its molecular weight

Composition of mixture: (mass fraction, mole fraction and average molecular weight):

Process streams often consist of mixtures or solutions of species and the relative amount of each species
is quantified by expressing the composition/concentration of that particular species. Following terms are
used to define composition of mixture consisting of species A, B, C, ......:

Mass fraction:

mass of A kg A gA lb A
𝑥𝑥𝐴𝐴 = � or or �
total mass kg total g total lb total
Mole fraction:

moles of A kmol A mol A lb-mol A

𝑦𝑦𝐴𝐴 = � or or �
total moles kmol total mol total lb-mol total

It is evident from the above two definitions of mass and mole fractions that:
𝑁𝑁 𝑁𝑁

� 𝑦𝑦𝑖𝑖 = 1; � 𝑥𝑥𝑖𝑖 = 1
𝑖𝑖=1 𝑖𝑖=1

�)
Average molecular weight of mixture ( 𝑴𝑴

Consider 1 mole of mixture of N species with mole fractions as y 1 , y 2 , y 3 .......y N .

=> we have y 1 moles of species-1, y 2 moles of species-2, y 3 moles of species-3 and so on.

=> y 1 M 1 grams of species-1, y 2 M 2 grams of species-2, y 3 M 3 grams of species-3, and so on

mass of mixture sample 𝑦𝑦1 𝑀𝑀1 + 𝑦𝑦2 𝑀𝑀2 + 𝑦𝑦3 𝑀𝑀3 + ⋯

�=
𝑀𝑀 =
total number of moles 1
𝑁𝑁
� = � 𝑦𝑦𝑖𝑖 𝑀𝑀𝑖𝑖
𝑀𝑀
𝑖𝑖=1

Where M i is the molecular weight of pure species i.

Similarly, if mass fractions are known:

𝑁𝑁
1 𝑥𝑥𝑖𝑖
=�
�
𝑀𝑀 𝑀𝑀𝑖𝑖
𝑖𝑖=1

Note about convention generally followed: Composition of gases will always be presumed to be given
in mole% or fraction unless specified otherwise. Compositions of liquids and solids will be given as wt%
or mass fraction unless specifically stated otherwise.

Mass concentration: mass of component i per unit volume of mixture (units as g/cm3, kg/L, etc.).

Molar concentration: moles of component i per unit volume of mixture (units as mol/L, lb-mol/ft3).

Molarity: molar concentration of solute expressed as g-moles of solute per liters of solution.

Parts per million (ppm) and parts per billion (ppb): Both of these are used to express the
concentration of trace species i.e species which are present in very small amount in a mixture. ppm (ppb)
refers to number of parts present per million (billion) of a mixture. ppm or ppb may refer to mass or mole
ratio, however, as per the convention; they refer to mole ratios for gases and mass ratios for liquid
mixtures unless otherwise stated. Example: 15 ppm of SO 2 in air means 15 mol of SO 2 are present in 106
moles of air.
Problem: A commercially available chemical contains 4.2 kg of Na 2 CO 3 , 0.2 kg HCl & 5.8 kg water.
Determine its composition in mass fraction and mole fraction and also calculate its average molecular
weight. Molecular weight of Na 2 CO 3 is 106 g/mol, HCl is 36.5 g/mol, water is 18 g/mol

Solution:

Total mass = 4.2 + 0.2 + 5.8 = 10.2 kg

Mass fractions denoted as 𝑥𝑥𝑖𝑖 and mole fractions as 𝑦𝑦𝑖𝑖

4.2
𝑥𝑥𝑁𝑁𝑎𝑎 2 𝐶𝐶𝑂𝑂3 = = 0.412 kg 𝑁𝑁𝑎𝑎2 𝐶𝐶𝑂𝑂3 /kg
10.2
0.2
𝑥𝑥𝐻𝐻𝐻𝐻𝐻𝐻 = = 0.019 kg HCl/kg
10.2
5.8
𝑥𝑥𝑤𝑤𝑤𝑤𝑤𝑤𝑤𝑤𝑤𝑤 = 1 − 0.412 − 0.019 or = 0.569 kg 𝐻𝐻2 𝑂𝑂/kg
10.2
Assume 1 kg of chemical:

⇒ 0.412 𝑘𝑘𝑘𝑘 𝑁𝑁𝑎𝑎2 𝐶𝐶𝑂𝑂3 , 0.019 𝑘𝑘𝑘𝑘 𝐻𝐻𝐻𝐻𝐻𝐻, 0.569 𝑘𝑘𝑘𝑘 𝑊𝑊𝑊𝑊𝑊𝑊𝑊𝑊𝑊𝑊

412 g 19 569
⇒ , mol HCl ; 𝑚𝑚𝑚𝑚𝑚𝑚 𝑤𝑤𝑤𝑤𝑤𝑤𝑤𝑤𝑤𝑤
106 𝑔𝑔 𝑁𝑁𝑎𝑎2 𝐶𝐶𝑂𝑂3 /𝑚𝑚𝑚𝑚𝑚𝑚 𝑁𝑁𝑎𝑎2 𝐶𝐶𝑂𝑂3 36.5 18

⇒ 3.887 𝑚𝑚𝑚𝑚𝑚𝑚 𝑁𝑁𝑎𝑎2 𝐶𝐶𝑂𝑂3 ; 0.521 𝑚𝑚𝑚𝑚𝑚𝑚 𝐻𝐻𝐻𝐻𝐻𝐻; 31.611 𝑚𝑚𝑚𝑚𝑚𝑚 𝑤𝑤𝑤𝑤𝑤𝑤𝑤𝑤𝑤𝑤

𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇 𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚 = 36.019 𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚

3.887 𝑁𝑁𝑎𝑎2 𝐶𝐶𝑂𝑂3

𝑦𝑦𝑁𝑁𝑎𝑎 2 𝐶𝐶𝑂𝑂3 = = 0.108 mol
36.019 𝑚𝑚𝑚𝑚𝑚𝑚
0.521
𝑦𝑦𝐻𝐻𝐻𝐻𝐻𝐻 = = 0.014 mol HCl/mol
36.019

𝑦𝑦𝑤𝑤𝑤𝑤𝑤𝑤𝑤𝑤𝑤𝑤 = 1 − 0.108 − 0.014 = 0.878 mol water/mol

Problem: A 1.5 molar aqueous solution of hydrochloric acid flows into a process unit at a rate of
1.5m3/min. The specific gravity of solution is 1.05. Calculate (i) the mass concentration of HCl in kg/m3,
(ii) the mass flow rate of HCl in kg/s, and (iii) mass fraction of HCl.
Solution:
(i)
1.5 𝑚𝑚𝑚𝑚𝑚𝑚 𝐻𝐻𝐻𝐻𝐻𝐻 36.5 𝑔𝑔 𝐻𝐻𝐻𝐻𝐻𝐻 1 𝑘𝑘𝑘𝑘 103 𝐿𝐿
1.5 𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚 𝑠𝑠𝑠𝑠𝑙𝑙 𝑛𝑛 = × × × = 54.75 kg/m3
1 𝐿𝐿 𝑠𝑠𝑠𝑠𝑙𝑙 𝑛𝑛 1 𝑚𝑚𝑚𝑚𝑚𝑚 𝐻𝐻𝐻𝐻𝐻𝐻 103 𝑔𝑔 1 𝑚𝑚3
(ii)
1.5 𝑚𝑚3 54.75 𝑘𝑘𝑘𝑘 1 𝑚𝑚𝑚𝑚𝑚𝑚
𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚 𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓 𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟 = × × = 1.369 kg HCl/s
min 1 𝑚𝑚3 𝑆𝑆𝑆𝑆𝑙𝑙 𝑛𝑛 60 𝑠𝑠
(iii)
SG = 1.05 ⇒ 𝜌𝜌 = 1050 kg sol/m3
1.5 𝑚𝑚3 𝑠𝑠𝑠𝑠𝑙𝑙 𝑛𝑛 1050 𝑘𝑘𝑘𝑘 𝑠𝑠𝑠𝑠𝑙𝑙 𝑛𝑛 1min
kg/s of solution = × × = 26.25 kg sol𝑛𝑛 /s
min 𝑚𝑚3 𝑠𝑠𝑠𝑠𝑙𝑙 𝑛𝑛 60 𝑠𝑠
(1.369 kg Hcl/s)
𝑥𝑥𝐻𝐻𝐻𝐻𝐻𝐻 = = 0.0522 kg Hcl/kg solution
(26.25 kg sol𝑛𝑛 /s)
Problem: A lethal dose for hydrogen cyanide (HCN) in air is 300 mg/kg of air at room temperature and
the safe limit of HCN for an 8-hour exposure is 10 ppm. Convert 10 ppm in mg HCN/kg air and compare
it with lethal dose for HCN.
Solution:
10 𝑚𝑚𝑚𝑚𝑙𝑙 𝐻𝐻𝐻𝐻𝐻𝐻
10 𝑝𝑝𝑝𝑝𝑝𝑝 𝐻𝐻𝐻𝐻𝐻𝐻 = 6
10 𝑚𝑚𝑚𝑚𝑚𝑚 (𝑎𝑎𝑎𝑎𝑎𝑎 + 𝐻𝐻𝐻𝐻𝐻𝐻)
10 𝑚𝑚𝑚𝑚𝑚𝑚 𝐻𝐻𝐻𝐻𝐻𝐻 27 𝑔𝑔 𝐻𝐻𝐻𝐻𝐻𝐻 1 𝑚𝑚𝑚𝑚𝑚𝑚 𝑎𝑎𝑎𝑎𝑎𝑎 1000 𝑚𝑚𝑚𝑚 𝐻𝐻𝐻𝐻𝐻𝐻 1 𝑔𝑔 𝑎𝑎𝑎𝑎𝑎𝑎
= × × × × −3
106 𝑚𝑚𝑚𝑚𝑚𝑚 𝑎𝑎𝑎𝑎𝑎𝑎 1 𝑚𝑚𝑚𝑚𝑚𝑚 𝐻𝐻𝐻𝐻𝐻𝐻 29 𝑔𝑔 𝑎𝑎𝑎𝑎𝑎𝑎 1 𝑔𝑔 𝐻𝐻𝐻𝐻𝐻𝐻 10 𝑘𝑘𝑘𝑘 𝑎𝑎𝑎𝑎𝑎𝑎
= 9.31 mg HCN/kg air
9.31
𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟 𝑤𝑤. 𝑟𝑟. 𝑡𝑡 𝑙𝑙𝑙𝑙𝑙𝑙ℎ𝑎𝑎𝑎𝑎 𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑 = = 0.031
300
10 ppm is significantly less than lethal dose of 300 mg HCN/kg air.
Unit's summary:

In the present unit, we will discuss the basic functions of different equipments/units which are frequently
encountered in chemical engineering process industries. We do not attempt to describe any equipment in
detail, but will give a brief idea about the purpose for which the equipment is used, basic principle of
operation, and a figure/schematic/block-diagram with possible input and output process streams.

Divider/Splitter: A divider or splitter is simply a pipeline or stream which is bifurcated into two or more
streams to deliver material to multiple units. In the figure given below, stream is divided into two streams
B and C. Note that since streams are simply divided and no other processing is involved, the compositions
of each of the three streams will remain same. We will see it later that we can write down only one
independent material balance for splitter. Flow rates of streams A, B, and C may be different.

Mixer or Blender: As the name suggests, a mixer is used to mix two or more liquids/gas or solutions.
The schematic and block-diagram of a continuous mixer is shown below. Two or more feed streams could
be present and there will be usually one exit mixed stream. A stirrer is used to mix the components from
different feed streams and hence, a work transfer term will be present which must be accounted for while
performing energy balances.

For material balance, the mixing process is usually represented as:

Dryer (drying process): The process of drying involves removal of water (or any other liquid) by heating
a substance which could be solid, or semi-solid. For example, heating wet wood chips to remove moisture
from wood chips. The block diagram of this process is shown below:

Filtration process: Recall the use of filter paper in chemistry lab experiments. The filtration process does
the same in continuous or semi-continuous manner. A slurry (concentrated solution of a solid particles
dispersed in a liquid) is passed through a filter cloth (or medium) resulting in trapping of solid particles
by filter cloth and allows the liquid which is free of solids (clear liquid known as filtrate) to pass through.
The solids deposited on filter cloth are referred as filter cake. The schematic of filtration unit is shown
below:

As an example of the case where the feed solution contains solid which are also soluble in liquid,
consider a feed which is a salt solution containing salt crystals as solid particles. When such feed solution
passes through filter cloth, the solid crystals are retained by filter cloth while the filtrate passes though the
filter unit. In this case, the filter, even though free of solids salt crystals, will contains dissolved salt in it.
In a similar fashion the wet filter cake consists of solid crystals plus a solution of salt that wets the solid
crystals.

Distillation column: Distillation is a method of separating chemical species based on differences in

tendency to vaporize at a given temperature (or to be precise on their volatility). Roughly speaking, lower
the boiling point of a species higher is the tendency to vaporize (or higher volatility). A schematic of
distillation column is shown below:
The feed mixture enters the column in which it is partially vaporized. The vapors move upward and
consist of majority of more volatile components while the liquid fall downwards and consists of majority
of less volatile components. The temperature in the column is lowest at top and increases to highest at
bottom. At each downward section, more and more vapors are generated from the falling liquid which
moves upwards towards top. The vapors collected at the top are condensed and a portion of it is recycled
back to the column and rest is collected as product. The product collected from the top is called as
distillate and the recycled stream is called as reflux stream. The liquid collected at the bottom (majorly
consisting of less volatile component) is sent to a re-boiler. The vapors generated in re-boiler are sent
back to column while the liquid is collected as bottoms product. The distillation unit itself is multi-unit
system comprising of a column (where distillation is going on), a re-boiler, and a condenser.

Evaporator: An evaporator is essentially used to concentrate solutions, for example, concentrating salt
solution by evaporating water or concentration of fruit juices by evaporating water etc. The block diagram
of evaporator looks similar to a dryer except that the solid are not present anywhere or all process streams
are either liquid or vapors.
Absorption (and desorption): Absorption is used to remove a component from gas mixture by
contacting the gas mixture with a suitable liquid solvent in which that particular component is soluble. An
example in the figure below shows the absorption of volatile organic compounds (VOCs) using oil as
solvent. The gas mixture containing VOCs flowing upwards in the column comes in contact with liquid
solvent flowing downward and in the process selectively absorbs VOC components from the gas stream.
The column is designed in such a way that nearly clean air leaves from the top of the column and the
liquid leaving from the bottom is rich in VOCs.

Reactor: As the name suggests, a reactor is used to carry out a desired reaction. There are several types
of reactors such as mixed flow reactor, plug flow reactor, fluidized bed reactor, etc., however, in this
course we are not concerned with the type of reactor. Our point of interest is simply that a reactant stream
enters in the reactor and undergoes reaction(s) and gets converted into product species. The block diagram
for the reactor is shown below:

Heat exchanger: is equipment used to heat (cool) a cold (hot) fluid by using a hot (cold) fluid without
actually bringing the two fluids in physical contact with each other. A simple figure for heat exchanger is
shown below. The heat exchanger consists of a large cylindrical shell with tubes fitted in it. SO 3 enters in
inner tubes at 700 K and leaves the unit at 420 K. The SO 3 is cooled using a shell side fluid (SO 2 ) which
enters at 350 K and leaves at 630 K. There are various designs and types of heat exchangers, however, in
the present course, we are only interested in the inlet and outlet streams and are not at all concerned with
the details of internal design of any unit.
Note: In the above discussion, we have provided a brief description of some of the frequently used
equipments in chemical process industry. It is important to point out that while the detail design is crucial
for actual operation, it is not required to go into these details for the purpose of this course. In context of
present course, the key points to note are: (i) input and output streams, (ii) identification of components in
different input and output streams, (iii) identification of phases of substances which are present in input
and output process streams, and (iv) given an objective or change undergone by a substance, selection of
appropriate unit for that change or process. As an example, consider the following problem description:
Problem: Suggest equipment(s) for the following processes:

1. For converting N 2 and H 2 to NH 3 .

2. Acetone is to be removed from air to get clean air.
3. A liquid hydrocarbon feed consisting mixture of n-heptane, n-hexane, and n-octane is to be
separated into two fractions such that one fraction contains majorly n-hexane and the other
contains maximum of octane. The normal boiling points of n-hexane, n-heptane, and n-octane
respectively are 69oC, 98oC, and 125oC.

Solution:

1. We are required to carry out a reaction: N 2 + 3H 2 --> 2 NH 3 , thus, a reactor must be used.
2. Acetone is to be recovered from a gas stream. This can be achieved by using a liquid solvent in
which acetone can be preferentially dissolved. Thus, we will use an absorber.
3. The given mixture has differences in boiling point and hence different tendency to vaporize at
given temperature. Hence, a distillation column will be used.
Problem: Potassium chromate salt crystals are produced from the salt solution by lowering the solution
temperature. The lowering of temperatures causes a decrease in solubility and causes salt crystals to
precipitate in the vessel. A salt solution is continuously fed to a vessel which is kept at lower temperature
to cause crystallization of the salt. The solution containing solid crystals leaves the vessel and enters a
filter unit to separate solid crystals from liquid solution. Draw the block diagram for the process
mentioning all the process streams.

Solution:

Note that the vessel in which crystals are formed can be called as a crystallization unit or simply
crystallizer. The unit that follows this crystallizer is a filtration unit.
 Material Balance Fundamentals- Non-reactive Systems
(Guidelines for solving MB problems)
All problems related to material and energy balance calculations will typically involve the
following: Given a process description with some known quantities (flow-rates, amounts of mass,
temperature, pressure, etc. of some streams) and unknown variables (flow-rates, amounts of mass,
temperature, pressure, etc.), calculate the unknown variables. We have already discussed one
example in previous unit on writing down material balance calculations for a batch and a
continuous mixing process. Knowingly or unknowingly, we have followed a strategy while
applying material balances for the previous example. In this unit, we will outline the procedure that
is to be followed for any material balance (later energy balance as well) problem. After carefully
reading the problem statement, four steps are always involved in any material balance problem:
1. Drawing the sketch of the process and labelling the process diagram (or drawing of
completely labelled flowchart).
2. Choosing a basis of calculation.
3. Performing degree of freedom analysis.
4. Writing down equations to solve for unknown variables.
Flowcharts:
During this course, we will often encounter problems statements of the following type:
100 mol/h of propane and 4760 mol/h of air are fed to combustion chamber. The gases from the
combustion chamber were analyzed and it was found to contain 50 mol/h of propane. These gaseous
products were sent to a condenser to remove water and the gases then goes to other unit for further
processing. Calculate the unknown flow-rates of each component in this two-unit process.
Now, consider the block diagram shown in Figure – 2.1, which depicts all the information provided
in the above statements in a much more organised manner. Note that by having a look at this
diagram; one can very clearly see the known quantities and the variables that are required to be
calculated. These block diagrams are referred as flowcharts in this course. We simply use boxes
to represent different units/equipments (like reactor, combustion furnace, distillation column, etc.)
and lines with arrows to represent different streams carrying material/species in and out of the
process. For example, in Figure - 2.1, two streams containing 100 mol/h propane and 4760 mol/h
air enters the combustion chamber and the exit stream contains propane, oxygen, nitrogen, carbon
dioxide, and water. Similarly, there is one inlet and two exit streams for condenser. Each steam in a
flowchart should be labelled which includes identification of all the components (species) in each
stream and mentioning the amount/flow-rate of each specie present in that particular stream. Thus,
we refer a flowchart as completely labelled if all the streams in a flowchart are labelled i.e., if we
can express the amount (mass or moles) or flow-rates (mass or molar flow-rate) of each species in
each stream in terms of labelled quantities (known values or unknown variables).

Figure - 2.1
Figure - 2.2 shows the complete labelling of the process shown in Figure - 2.1. Note that we can
express the flow-rate of each species in each stream. For example, 100 mol/h propane in one of the
feed stream to combustion chamber (known value) while n1 mol/h O2, n2 mol/h N2, etc. for the exit
stream of combustion chamber (unknown variables).

Figure 2.2: Completely labelled flowchart

The labelling of flowchart simply means labelling of all the streams involved in the process. Thus, a
stream containing 10 mol% ethane and 90 mol% methane at 100oC and 2 atm flowing at a rate of
100 mol/h will be labelled as:

100 mol/h
0.10 mol Ethane/mol
0.90 mol Methane/mol
100oC, 2 atm

If the flow-rate was not known in above case, then the stream would be labelled by assigning a
variable to the flow-rate and will be shown as:
n mol/h
0.10 mol Ethane/mol
0.90 mol Methane/mol
100oC, 2 atm

On the other hand, if mole fractions were unknowns:

100 mol/h
y mol Ethane/mol
(1-y) mol Methane/mol
100oC, 2 atm

Note that we have used the constraint that sum of all mole fraction must be unity to reduce the
number of unknown variables in labelling of a process stream. Reducing the number of unknown
variables is usually helpful and should be taken care of wherever possible. For example, if it is
given that the flow rate of stream - 1 is double the flow-rate of stream - 2, then, instead of taking
flow-rates as m1 kg/h and m2 kg/h, it is better to use m kg/h for stream - 2 and 2m kg/h for stream -
1. Further, as balances are not usually written for volumes, it is usual practice to label mass or molar
flow-rates whenever volumetric flow-rates are known for a process stream.
Problem: A liquid mixture containing 20% Benzene (B), 40% Toluene (T), and 40% Xylene (X) by
mass is fed to a distillation column operating at steady state. The overhead product stream (stream
leaving the top of the column) contains 95% Benzene, 5% Toluene, and no Xylene while the bottom
product stream contains 2% Benzene. The volumetric flow-rate of feed stream is 1000 L/h and the
specific gravity of the feed mixture is 0.875. Calculate the mass flow-rate of overhead product
stream and mass flow-rate and composition of bottom stream.
Solution:

The labelled flowchart is shown above. Few points are worth to note about the labelling of the
above process:
i. Since, volumetric flow-rate is given in units of L/h, therefore, the mass flow-rates are
labelled in units of kg/h.
ii. Specific gravity of feed mixture is known means that we will be able to calculate mass flow-
rate of feed stream (i.e. variable m).
iii. There are two ways in which the overhead and product stream could be labelled: (a) as
shown above in terms of total flow-rate of a particular stream and its composition, and (b) in
terms of individual component flow-rate of each stream i.e. m1B kg B/h, m1T kg T/h for
overhead stream and m2B kg B/h, m2T kg T/h, and m2X kg X/h for bottom stream. However,
we preferred scheme (a) because the composition of overhead stream is known completely
while benzene composition was known for bottom stream. In case, compositions were not
mentioned for these two streams, we would have preferred scheme (b). This point will
become clearer as we take more problems in this course.

Density of feed mixture = ρ = SG ×ρwater = 0.875×1 kg/L = 0.875 kg/L

m = 1000 × 0.875 = 875 kg/h
Balance Equation: input - output + generation - consumption = accumulation
Accumulation = 0 (steady state)
Generation and consumption = 0 (non-reactive system)
Thus, balance equation: input = output

Total Balance: m = m1 + m2 875 = m1 + m2

Benzene Balance: 0.2×875 = 0.95×m1 + 0.02×m2
Solving these two equations simultaneously: m1 = ; m2 =
Toluene balance: 0.4×875 = 0.05m1 +xTm2 xT =
Thus, mass flow-rate of overhead product stream =
Mass flow-rate of bottom stream =
Composition of bottom stream =
Basis of calculation: is the reference selected for the calculations in a particular problem. For
example, in previous example, we have performed calculations for a given volumetric feed flow
rate of 1000 L/h. If stream amount or flow-rate is given in a problem, we usually select this amount
or flow-rate as the basis of calculation. Thus, the basis of calculation selected was 1000 L/h of inlet
feed (not explicitly mentioned in the solution). If the amount or stream flow-rate for any stream in a
process is not known, a basis of calculation is usually chosen to perform calculations. For example,
if the inlet feed flow-rate was not known in the above problem, we would have selected 100 kg/h of
inlet feed flow-rate as basis of calculation and then proceeded to determine other unknowns, i.e.,
overhead flow-rate, bottom flow-rate and compositions. Of course, this will change the values of m1
and m2, but not the compositions. We would still have obtained the same value of xT. Note that we
have three choices to select the basis of calculations in the above problem: (i) m = 100 kg/h as done
above, (ii) m1, or (iii) m2. While one can choose any of the three as basis of calculation, however,
we usually choose flow-rate or amount of a process stream with known compositions as basis of
calculation. This usually makes the calculation easy. Thus, either of m or m1 is a convenient option
for being the basis of calculations as the compositions of both the streams are known. Similarly, it is
because of this convenience that we have chosen 100 kg/h, and not any number like 1236 kg/h or
1983 kg/h etc, which again makes calculations of amounts of component in a stream relatively easy.
On the other hand, considering 1000 L/h equivalent to 875 kg/h of inlet flow-rate, we could scale up
or scale down the balanced process to some other value of feed flow-rate. For example, if we want
to perform calculations for a feed flow-rate of 100 kg/h for the above problem, we do not require
redoing all the calculations. We could scale down the process as:
Scale (down) ratio = new flow-rate/old flow-rate = 100/875 = 0.1143
m1new = 0.1143 m1, m2new = 0.1143 m2
The compositions will remain identical as given in the above flow-chart or as calculated.
Check this yourself by redoing the calculation with inlet feed flow-rate as 100 kg/h and compare it
with the values obtained by scaling procedure. It is important to mention here that scaling up or
down a balanced process flowchart assumes that efficiency of all equipments remains
unchanged.
Another simple example of scale-up is shown in the flowchart given below:

It is required to achieve the same separation with a continuous feed of 525 lb-mol/h.
Thus, scale ratio = 525(lb-mol/h)/100 (mol/h) = 5.25 lb-mol/mol
Feed = (100 mol/h) ×5.25 (lb-mol/mol) = 525 lb-mol/h
Top product = (50 mol/h) ×5.25 (lb-mol/mol) = 262.5 lb-mol/h
Bottom product: (15 mol-A/h) ×5.25 (lb-mol/mol) = 78.75 lb-mol A/h
(35 mol B/h) ×5.25 (lb-mol/mol) = 183.75 lb-mol A/h
The flowchart for scaled process is:
Degree of Freedom Analysis: Degree of freedom (DOF) analysis helps in determining wheteher
the given information in a problem is sufficient to solve it or not.
DOF = number of unknowns (NU) - number of independent equations (NE)
DOF = NU - NE.
Three cases arise:
i. DOF = 0; this implies that there are equal number of unknowns and equal number of
independent equations which means that the problem can be solved
ii. DOF > 0; NU > NE, this means more number of unnowns than independent equations. This
implies that at least additional variables equal to DOF must be supplied before remaining
variables can be solved. There is no point in doing any calculations unless more variables
are specified.
iii. DOF < 0; this means more independent equations than unknowns. Either the flowchart is
incomplete or the problem is overspecified with redundant or possibly incosistent relations.
In this case as well, there is no point in performing any calculations.

Generating Equations and Solving for Unknowns: The final task is to write down equations
involving unknown variables and solving them to find all unknowns. Equations are generated from
the following sources:
i. Material Balances are the primary source of equations. For a non-reactive system, the
number of independent material balances is equal to the number of components present in
a system. For example, in the previous problem concerning the separation of a liquid
mixture conatining three components benzene, tolune and xylene; three independent
material balance equation can be generated. Note that we could generate more number of
equations like: total balance, benezene, xylene, and toluene balances (or simply carbon,
hydrogen balance etc). However, out of all the equations generated, only three equations
will be independent equations. If we consider writing total, benzene, toluene, and xylene
balance:
Total Bal: (1) m= m1 + m2
Benzene Bal: (2) =
0.2m 0.95m1 + 0.02m2
Toluene Bal: (3) =
0.4m 0.05m1 + xT m2
Xylene Bal: (4) 0.4m =−
(1 0.02 − xT )m2

Note that if we add Eq. (1), (2), and (3); we obtain Eq. (4) or (1) - (2) - (3) = (4). Thus, out
of these four equations, only three are independent equations. We will discuss the
determination of independent material balances for reactive systems later.
ii. Energy Balance will provide one more equation; however, we will discuss it later.
iii. Process specification like relation between flow-rates of two stream is specified in problem
statement (amount of stream 1 is double the stream 2; 2 m2 = m1), or any other specification
relating unknown and/or known variables.
iv. Physical properties and laws like specification of density, specific gravity which allows
 conversion between volumetric flow-rate to mass flow-rate; or an equation of state for gases
(to be discussed later) relating number of moles to pressure, temperature and volume.
v. A physical constraint like sum of mole fractions of all components is unity etc.

We can now revisit the distillation problem keeping in mind the above discussion:

Problem: A liquid mixture containing 20% Benzene (B), 40% Toluene (T), and 40% Xylene (X) by
mass is fed to a distillation column operating at steady state. The overhead product stream (stream
leaving the top of the column) contains 95% Benzene, 5% Toluene, and no Xylene while the bottom
product stream contains 2% Benzene. The volumetric flow-rate of feed stream is 1000 L/h and the
specific gravity of the feed mixture is 0.875. Calculate the mass flow-rate of overhead product
stream and mass flow-rate and composition of bottom stream.
Solution:
Step 1: Basis of calculation: 1000 L/h of inlet feed

Step 2: Labelled flowchart:

Step 3: DOF analysis:

DOF = nU − nE = 4(m, m1 , m2 , xT ) − 3 MB(B, T, X or total, B, T or total, X, T) − 1(S.G.)=0
DOF = 0 implies that the system is solvable. In the above expression for DOF, MB stands for
material balances, and S.G. stands for specific gravity. We will frequently use these abbreviated
form to save space and time. Note that we have not just mentioned that there are 4 unknowns, but
also mentioned within bracket the unknowns that are required to be calculated. Similarly, we have
written down inside bracket that which three equations (and process specification) can be generated
to solve for unknowns.
Now the solution procedure is immediately clear. We first use SG to calculate feed mass flow-rate
(m), and then apply material balances to solve the rest of unknowns (3 MB for three unknowns: m1,
m2, and xT).
Density of feed mixture = ρ = SG ×ρwater = 0.875×1 kg/L = 0.875 kg/L
m = 1000 × 0.875 = 875 kg/h
Total Balance: m = m1 + m2 875 = m1 + m2
Benzene Balance: 0.2×875 = 0.95×m1 + 0.02×m2
Solving these two equations simultaneously: m1 = ; m2 =
Toluene balance: 0.4×875 = 0.05m1 +xTm2 xT =
Thus, mass flow-rate of overhead product stream =
Mass flow-rate of bottom stream =
Composition of bottom stream =
Important note about writing independent material balances:
1. For a non-reactive system, the maximum number of independent material balances will be
equal to the number of components present in the system.
2. If two components are present in the same ratio wherever they occur in the process, then,
only one independent balance can be written out of these two components.
Problem-1: Draw and label the following given streams:
i. An aqueous solution of NaCl, and KCl flowing to an evaporator.
ii. A gas stream containing sulfur trioxide and air flowing at a rate of 250 mol/h/.
Solution:
i. There are two ways in which this stream can be labelled.

Figure 2.2.1
For first scheme, kg/h NaCl = mx1 , kg/h KCl = mx2 , and kg/h water = m(1 − x1 − x2 ) . On the
other hand, for second labelling scheme, the mass flow-rates of each component is
mentioned explicitly.
ii. Two possible ways in which the stream can be labelled:

Figure 2.2.2
Note that in first scheme, we use an additional equation for composition of air; while in
second scheme the composition of oxygen and nitrogen in air are explicitly mentioned in
labelling. Second scheme eliminates one unknown and one additional equation, and hence is
preferred over first scheme.
 Problem-2: Consider the following steady state processes and determine whether the system is
solvable for all unknowns or not?
i.

ii.

Solution:
i. We need to calculate DOF to find if the system is solvable or not.
DOF= nU − nE
= 7( x12 , x43 , x24 , x34 , x44 , P, C ) − 4 MB(1,2,3,4 components)
= − 3(Σxi 1 for stream 1,3 and 4)
= 0 ⇒ Solvable

= nU − nE
DOF
=
ii. 4( x A , xB , P, F2 ) − 3 MB(on A, B, and C)
= 1 ⇒ Not solvable unless we specify one more variable
Problem-3: A stream of humid air containing 10 mol% water vapor enters a condensation unit in
which some amount of water vapor is condensed. The flow-rate of condensed water was measured
to be 250 L/h. Assuming steady state operation, calculate the flow-rate and composition of air
stream leaving the condenser.

Solution:
Step 1: Basis: 250 L/h of water condensed.
Step 2: Labelled flowchart: (HA = Humid Air, DA = Dry Air)

Figure 2.2.5
HA consists of DA and water vapor. DA consists of oxygen and nitrogen with 21 mol% and 79
mol%, respectively. However, the ratio of oxygen and nitrogen in both inlet and exit streams remain
identical; hence, the material balances on oxygen and nitrogen will be exactly identical (as shown
below).
input = output
Oxygen Balance: 0.9n1 × 0.21 = 0.21n3
Nitrogen Balance: 0.9n1 × 0.79 = 0.79n3
Thus, one can treat this system as containing two components: water and dry air.
Step 3: Degree of Freedom Analysis:
DOF= 4unknowns(n1 , n2 , n3 , n4 ) − 2MB(Water and DA) − 1(water density to find n2 )
=1
Thus, unless we specify one more condition or variable, we will not be able to solve this problem.

Consider that 95% of water present in the feed is condensed (thus, one more condition is specified),
this means that the DOF = 0 and hence, the system becomes solvable.
The labelled flowchart, with new specification and considering HA being only composed of two
components i.e. dry air and water, is shown below:
 Figure 2.2.6

Step 4: Writing balances

kg L 1 kmol
ρ H O(l) = 1 kg/L ⇒ n2 = 1 × 250 × = 13.89 kmol/h
2
L h 18 kg
95% specification: 0.1n1 × 0.95 = n2 ⇒ n1 = 146.21 kmol/h
water balance: 0.1n1 =n2 + n4 ⇒ n4 =0.731 kmol/h
DA balance: 0.9n1 = n3 ⇒ n3 = 131.589 kmol/h
 Material Balance Fundamentals- Non-reactive Systems
(Balances on multiple unit system)

Consider the process (non-reactive) shown in Figure - 2.3.1. The variables for Feed-2, Pdt-1, Pdt-2, and
one intermediate stream are completely specified while variables for Feed-1, Pdt-3, and one intermediate
stream are not specified. Our aim is to calculate the unknown variables for this process.

Figure - 2.3.1
Off course, the first step is labeling of flowchart and the fully labeled flowchart is shown in Figure - 2.3.2.
Note that, since, the process involves either mixing or separation of two components (A and B), the
unspecified streams will also contain only these two components. The steps remain identical as for the
case of single unit system i.e. (i) drawing of labeled flowchart, (ii) choosing a basis of calculation, (iii)
performing degree of freedom (DOF) analysis, and (iv) writing down independent equations. However,
instead of a single unit, we now have multiple units or multiple systems on which material balances can
be written. Some of the choices of the systems are shown by dashed boxes in Figure - 2.3.2. For example,
A is overall process as one system, B and D are unit-1 and unit-2 chosen as system, and C is the mixing
point on which one can write mass balance equations. Note that one can choose combination of different
units as one system, for example, unit-1 and mixing point combined can also be treated as one system.
However, usually this is not required.

Figure - 2.3.2
Thus, we are already done with step-1 (completely labeled flowchart). The step-2 involves choosing a
basis and for this we can conveniently choose 30 kg/h of Feed-2 stream as basis of calculations.

Step-3: DOF Analysis: Recall that for a single unit system, DOF informs us about the solvability of the
system. For multi-unit system, DOF analysis gives information about the solvability as well as the order
in which we have to write down material balance equations on different subsystems. We first determine
DOF for overall system and each sub-system present in the process. For the process shown in Figure -
2.3.2, it means system A (overall), B (unit-1), C (mixing point), and D (unit-2). Note that while
calculating DOF for a particular system, only those streams are to be taken into account which intersect
the boundary of the system under consideration. Thus, for overall system, Feed-1, Feed-2, Pdt-1, Pdt-2,
and Pdt-3 variables are to be taken into consideration in calculating DOF. On the other hand, for unit-1,
Feed-1, Pdt-1, and int-1 are considered. Recall, number of independent material balances for non-reactive
system is equal to number of components present in the system.

DOF for overall system = 4 unknowns (m1, x1, m3, x3) - 2 independent Material balances (MB) = 2 ≠ 0 ⇒
not solvable (requires two more specifications).

DOF for unit-1 = 4 unknowns (m1, x1, m2, x2) - 2 independent Material balances (MB) = 2≠ 0 ⇒ not
solvable (requires two more specifications).

DOF for C = 2 unknowns (m2, x2) - 2 ind. MB = 0 ⇒ solvable. Thus, we can write two balances (A and
B, or total and A, or total and B) to solve for m2 and x2. These two variables can now be treated as known
variables for further analysis.

DOF for D (unit-2) = 2 unknowns (m3, x3) - 2 ind. MB = 0 ⇒ solvable.

We first solve for sub-system which has zero DOF (C and D in this case). We cannot start with overall
system or unit-1 in this problem (DOF ≠ 0). We start writing balances on systems C and D and solve for
unknown variables involved with these two sub-systems. Now, with some more variables known (m2, x2
and m3, x3 in this problem), we revisit the DOF analysis to find out the sequence in which other units
must be solved to determine all unknown variables.
Revisiting DOF analysis: Note that DOF for B or unit-1 was equal to 2 ⇒ we need to supply two more
variables in order to solve unit-1. Now, with m2 and x2 known, the DOF for unit-1 = 0.
Similarly, DOF for overall system was 2 and with m3 and x3 known, revised DOF for overall system
becomes zero.
Thus, we can either apply balances on unit-1 or overall system to solve for remaining unknown variables
i.e. m1 and x1.

Step-4: Calculations:
Balance on unit-C:
Total balance: 𝑚𝑚2 + 30 = 90⇒ 𝑚𝑚2 = 60 𝑘𝑘𝑘𝑘⁄ℎ
A balance: 𝑚𝑚2 𝑥𝑥2 + 30 × 0.3 = 90 × 0.255⇒ 𝑥𝑥2 = 0.2325 𝑘𝑘𝑘𝑘 𝐴𝐴/𝑘𝑘𝑘𝑘

Balance on unit-D:
Total balance: 𝑚𝑚3 + 30 = 90⇒ 𝑚𝑚3 = 60 𝑘𝑘𝑘𝑘⁄ℎ
A balance: 𝑚𝑚3 𝑥𝑥3 + 30 × 0.6 = 90 × 0.255⇒ 𝑥𝑥3 = 0.0825 𝑘𝑘𝑘𝑘 𝐴𝐴/𝑘𝑘𝑘𝑘

Balance on unit-B: (or could be written on overall system)

Total balance: 𝑚𝑚1 = 40 + 𝑚𝑚2 ⇒ 𝑚𝑚1 = 100 𝑘𝑘𝑘𝑘⁄ℎ
A balance: 𝑚𝑚1 𝑥𝑥1 = 40 × 0.9 + 𝑚𝑚2 𝑥𝑥2 ⇒ 𝑥𝑥1 = 0.4995 𝑘𝑘𝑘𝑘 𝐴𝐴/𝑘𝑘𝑘𝑘

Note that while performing calculations, we have always written total balance and one component (A in
this case) balance. We could have used A and B balance, but note that this would have yielded two
nonlinear independent equations. On the other hand, using total and A-balance yields two linear equations
in two unknowns. A linear equation more readily solvable than a nonlinear one, hence, we always take
care to write a set of linear equations wherever possible. Off course in certain cases, it is not possible to
avoid nonlinear equations.
Important Note: If two species (say 1 and 2) in a process are always present in the same ratio wherever
they appear in the process, the balances on these two species will yield a single equation. Thus, in such a
case, only one balance would be independent out of these two. For example, if two air (assumed to be
composed of O2 and N2) streams are mixed to get an output air stream, we can write only one independent
balance (air balance or N2 or O2 balance) as the ratio O2/N2 in all three streams remain identical (Verify
it).

Important Note:
We determined the sequence in which different systems must be solved in the above example. However,
it is not always possible to determine this sequence from a DOF analysis. Such cases arise when the DOF
of all the sub-system and overall system is nonzero, but still, one can generate as many independent
equations as the number of unknown variables. This issue will become clearer in one of the unit level
problem. At this point, we only address how to determine the total number of independent equations that
we can generate in the above problem.
Consider figure - 2.3.2. We have six unknowns( 𝑚𝑚1 , 𝑥𝑥1 , 𝑚𝑚2 , 𝑥𝑥2 , 𝑚𝑚3 , 𝑥𝑥3 ), so we require six independent
equations to solve for these six variables. We can write two independent MBs on unit-1, two on unit-C,
and two on unit-2. Now any other balance written for a combination of two or more units will not form
independent balance. For example, the balance equations for overall system-A can be always obtained as
sum of balances on unit-1, unit-2 and unit-C. Similarly, balance on a combination of unit-1 and unit-C
can be obtained by summing independent balances over unit-1 and unit-C. Thus, the maximum number
of independent balances in a multiple unit system is equal to the sum of number of independent
balances on each sub-unit which is present in the multi-unit system. For above problem, we have
three sub-units with a total of six independent balances (two for each sub-unit). Thus, the problem is
solvable (six unknown and six independent equations in these unknowns).
Problem 1: Consider the separation by multi-distillation unit shown in Figure 2.3.3. All flow-rates are in
mol/min and compositions are mole percent.

i. Complete the labeling of flowchart by assigning variables to all unknown quantities.

ii. Perform a degree of freedom analysis to determine whether the system is solvable or not. If
solvable, write in order the equations you would solve to calculate unknown process variables.
Underline each variable(s) for which you would solve. Do not perform any calculations.

Figure 2.3.3
Nu = Total no. of unknowns = 12 (Q2, Q3, Q4, Q5, Q6, XA5, XB5, XC5, XA6, XB6, XC6, XU)

NE = Total no. of independent equations = no. of independent equations on D1 + no. of

independent equations on D2 + no. of independent equations on D3.

= 4(on D1) + 4(on D2) + 4(on D3)

DOF= NV – NE = 12-12 = 0 => solvable

Now trying to determine sequence:

DOF for overall system = 4 unknowns (XU, Q2, Q3, Q4,) – 4 (independent material balance on
A, B, C and D) = 0

=> XU, Q2, Q3 and Q4 can now be considered known for further analysis.

DOF for D1 = 8 unknowns (Q5, Q6, XA5, XB5, XC5, XA6, XB6, XC6) – 4 independent material
balances (on A, B, C and D).

= 4 => not solvable.

DOF for D2 = 4 unknowns (Q5, XA5, XB5, XC5) – 4 independent material balances (on A, B, C
and D).
= 0 => solvable => Q5, XAS, XB5, XC5 can be solved.

DOF for D3 = 4 unknowns (Q6, XA6, XB6, XC6) – 4 independent material balances (on A, B,
C, D)

= 0 => solvable to find Q6, XA6, XB6, XC6.

Therefore, sequence will be overall D2 D3

Equations:

Balances on overall system:

Total: 150 = 40 + Q2 + Q3 + Q4

A: 150×0.15 = 40×0.6 + 0.2Q4 => Q4 known

B: 150×0.25 = 0.3Q2 + 0.2Q4 => Q2 known

C: 150×0.40 = 40XU + 0.45Q2 + 0.7Q3 + 0.1Q4

=> Use total balance and C balance to solve for Q3 and XC1

Balance on D2:

Total: Q5 = 40 + Q2 (Q2 unknown => Q5 calculated)

B: XB5×Q5 = 0.45Q2

A: XA5×Q5 = 0.6×40

C: XC5×Q5 = XU×40 + 0.45Q2

Balance on D3:

Total: Q6 = Q3 + Q4

A: XA6×Q6 = 0.2Q4

B: XB6×Q6 = 0.65Q4

C: XU×Q6 = 0.1Q4 + 0.7Q3

Problem 2: Figure shows the process for cleaning dirt from freshly mined ore so that the ore remain dirt
free in later processing units. 5000 kg/h of dirt is charged into a drum in which continuously flowing
water soak the ore on its way to a drain at the bottom of the drum. The drained water from the drum
contains 40% dirt. The cleaned wet ore from the drum is passed through a dryer to remove water. The
flow-rate of wet ore is 5165 kg/h and the flow-rate of clean dry ore from dryer is 4835 kg/h. The water
containing dirt is cleaned in a settler, where 90% of the dirt is removed. The water output stream from the
settler is sent back to the drum. In order to make up for the loss of water in dryer and settler, fresh make
up water is added to the drum along with mined ore. Assume first that no water is present in the dirt
removed in the settler and then consider the case when 5% of water entering into the settler is also
removed with the dirt (more realistic case).

i. Determine the sequence in which different units must be solved.

ii. Calculate all unknown variables.

Solution:

Step 1: Basis of calculation: 5000 kg/h of mined dirty ore (contd. On next page)
Step 2: Labeled flowchart as shown in Figure for first case of water free dirt stream from settler.

Step 3: DOF analysis

Unit Unknowns Equations DOF

Overall 4 (m1, xo1, m2, m4) 3 (dirt, water and ore balances) 1
Drum 6 (m1, xo1, xo2, m6, 3 (dirt, water and ore balances) 3
xd6, m3)
Dryer 2 (m2, xo2) 2 (water and ore balances) 0
Settler 4 (m3, m4, m6, xd6) 2 (dirt and water balances) + 1 1
relation = 3

Above table shows that dryer must be solved first. Thus, for revisiting the DOF analysis, we can consider
(m2, xo2) to be known for further analysis.

Note that Overall system has DOF = 1 and m2 is one of the unknown variables for this system. Thus, with
known m2 (after solving for dryer), DOF = 0 for overall system. Hence, the second system for which we
will write equations will be overall system. After solving for overall system, m1, xo1, m4 will be known
quantities. m4 occurs as an unknown in settler DOF expression. Hence, the revisited DOF = 0 for settler.
With settler, dryer and overall system solved, on can easily identify that the DOF for drum will be zero.
Thus, based on above discussion, the sequence must be: Dryer →Overall→settler.

For the sake of understanding, the above discussion is also presented in tabular form. The variables that
are calculated after writing equations for a particular system are marked as bold in table below.
 Unit Variables Equations DOF DOF Known
associated with (original) (revisited)
system
Dryer 2 (m2, xo2) 2 (water and ore balances) 0 0 (m2, xo2)
Overall 3 (m1, xo1, m2, m4) 3 (dirt, water and ore 1 0 (m1, xo1, m2, m4)
Recall m2 is known balances)
Settler 4 (m3, m4, m6, xd6) 2 (dirt and water 1 0 (m3, m4, m6, xd6)
balances) + 1 relation = 3
All variables are solved

Step 4: Writing equations and calculations

Note that in the following, we take care in writing down linear equation at maximum places as possible.

Balance on dryer:
𝑦𝑦𝑦𝑦𝑦𝑦𝑦𝑦𝑦𝑦𝑦𝑦
Total: (1) 5165 = 𝑚𝑚2 + 4835 �⎯⎯⎯� 𝑚𝑚2 = 330 𝑘𝑘𝑘𝑘/ℎ water vapor
𝑦𝑦𝑦𝑦𝑦𝑦𝑦𝑦𝑦𝑦𝑦𝑦
Ore: (2) 5165𝑥𝑥𝑜𝑜2 = 4835 �⎯⎯⎯� 𝑥𝑥𝑜𝑜2 = 0.936 kg ore/kg

Balance on Overall process:

𝑦𝑦𝑦𝑦𝑦𝑦𝑦𝑦𝑦𝑦𝑦𝑦
Water: (3) 𝑚𝑚1 = 𝑚𝑚2 �⎯⎯⎯� 𝑚𝑚1 = 330 kg/h water make up
𝑦𝑦𝑦𝑦𝑦𝑦𝑦𝑦𝑦𝑦𝑦𝑦
Ore: (4) 5000𝑥𝑥𝑜𝑜1 = 4835 �⎯⎯⎯� 𝑥𝑥𝑜𝑜1 = 0.967 kg ore/kg
𝑦𝑦𝑦𝑦𝑦𝑦𝑦𝑦𝑦𝑦𝑦𝑦
Total: (5) 5000 + 𝑚𝑚1 = 𝑚𝑚2 + 4835 + 𝑚𝑚4 �⎯⎯⎯� 𝑚𝑚4 = 165 kg/h dirt

Balance on settler:
𝑦𝑦𝑦𝑦𝑦𝑦𝑦𝑦𝑦𝑦𝑦𝑦
90% condition: (6) 𝑚𝑚3 𝑥𝑥𝑑𝑑3 × 0.9 = 𝑚𝑚4 �⎯⎯⎯� 𝑚𝑚3 = 458.33 kg/h
𝑦𝑦𝑦𝑦𝑦𝑦𝑦𝑦𝑦𝑦𝑦𝑦
Total: (7) 𝑚𝑚3 = 𝑚𝑚4 + 𝑚𝑚6 �⎯⎯⎯� 𝑚𝑚6 = 293.33 kg/h
𝑦𝑦𝑦𝑦𝑦𝑦𝑦𝑦𝑦𝑦𝑦𝑦
Dirt: (8) 0.4𝑚𝑚3 = 𝑚𝑚4 + 𝑚𝑚6 𝑥𝑥𝑑𝑑6 �⎯⎯⎯� 𝑥𝑥𝑑𝑑6 = 0.0625 kg dirt/kg

Note that we have not used drum as system to solve for any variable. Thus, balances on drum can be used
to cross-check our calculations (verify it!)
Case - b (assuming wet dirt from the settler) Labeled flowchart as shown in Figure

Step 3: DOF analysis

Unit Unknowns Equations DOF

Overall 5 (m1, xo1, m2, m4, 3 (dirt, water and ore balances) 2
m5)
Drum 6 (m1, xo1, xo2, m6, 3 (dirt, water and ore balances) 3
xd6, m3)
Dryer 2 (m2, xo2) 2 (water and ore balances) 0
Settler 5 (m3, m4, m5, m6, 2 (dirt and water balances) + 2 2
xd6) relation = 4

Revisit DOF analysis:

Unit Variables associated Equations DOF DOF Known

with system (original) (revisited
)
Dryer 2 (m2, xo2) 2 (water and ore balances) 0 0 (m2, xo2)
Overall 4 (m1, xo1, m2, m4, m5) 3 (dirt, water and ore 2 1 Not possible to
Recall m2 is known balances) find unknowns
Settler 5 (m3, m4, m5, m6, xd6) 2 (dirt and water 1 1 Not possible to
balances) + 2 relation = 4 find unknowns
Drum 6 (m1, xo1, xo2, m6, xd6, 3 (dirt, water and ore 3 3 Not possible to
m3) balances) find unknowns
Thus, it seems that it is not possible to find all unknowns in this case (except m2, xo). Note that we can
still find xo1 using ore balance on overall system, but not any other variables (m1, m4, m5). This, however,
does not help in solving variables pertaining to any other unit. The question then is: Is this system
unsolvable?

Let us look at DOF in terms of total number of unknowns and total number of equations we can generate
for the whole process.

𝑁𝑁𝑈𝑈 = 9(𝑚𝑚1 , 𝑥𝑥𝑜𝑜1 , 𝑥𝑥𝑜𝑜2 , 𝑚𝑚2 , 𝑚𝑚3 , 𝑚𝑚4 , 𝑚𝑚5 , 𝑚𝑚6 , 𝑥𝑥𝑑𝑑6 )

𝑁𝑁𝐸𝐸 = 3 (drum: water, dirt and ore balance) + 2 (dryer: water and ore balance)
+ 4 (settler: dirt and water balance, two relations) = 9

𝐷𝐷𝑂𝑂𝑂𝑂 = 𝑁𝑁𝑈𝑈 − 𝑁𝑁𝐸𝐸 = 9 − 9 = 0

This shows that the system is indeed solvable. It is simply that we cannot determine the sequence for easy
solving. We can write down all nine equations and solve for nine variables.

Step 4: Writing equations and calculations

Note that in the following, we take care in writing down linear equation at maximum places as possible.

Balance on dryer:
𝑦𝑦𝑦𝑦𝑦𝑦𝑦𝑦𝑦𝑦𝑦𝑦
Total: (1) 5165 = 𝑚𝑚2 + 4835 �⎯⎯⎯� 𝑚𝑚2 = 330 𝑘𝑘𝑘𝑘/ℎ water vapor
𝑦𝑦𝑦𝑦𝑦𝑦𝑦𝑦𝑦𝑦𝑦𝑦
Ore: (2) 5165𝑥𝑥𝑜𝑜2 = 4835 �⎯⎯⎯� 𝑥𝑥𝑜𝑜2 = 0.936 kg ore/kg

Balance on Overall process: (or we could use equations for drum)

Water: (3) 𝑚𝑚1 = 𝑚𝑚2 + 𝑚𝑚5

𝑦𝑦𝑦𝑦𝑦𝑦𝑦𝑦𝑦𝑦𝑦𝑦
Ore: (4) 5000𝑥𝑥𝑜𝑜1 = 4835 �⎯⎯⎯� 𝑥𝑥𝑜𝑜1 = 0.967 kg ore/kg

Total: (5) 5000 + 𝑚𝑚1 = 𝑚𝑚2 + 4835 + 𝑚𝑚4 + 𝑚𝑚5

Balance on settler:

90% condition: (6) 𝑚𝑚3 𝑥𝑥𝑑𝑑3 × 0.9 = 𝑚𝑚4

5% condition: (7) 𝑚𝑚3 (1 − 𝑥𝑥𝑑𝑑3 ) × 0.05 = 𝑚𝑚5

Total: (8) 𝑚𝑚3 = 𝑚𝑚4 + 𝑚𝑚5 + 𝑚𝑚6

Dirt: (9) 0.4𝑚𝑚3 = 𝑚𝑚4 + 𝑚𝑚6 𝑥𝑥𝑑𝑑6

Solving equations (3, 5 to 9) simultaneously gives values of all remaining unknowns.

kg kg kg kg
𝑚𝑚1 = 343.75 , 𝑚𝑚3 = 458.333 , 𝑚𝑚4 = 165 , 𝑚𝑚5 = 13.75 ,
h h h h
kg
𝑚𝑚6 = 279.58 , xd6 = 0.0656 kg dirt/kg
h
Problem-1: Consider an absorption unit for recovering ammonia from a gas stream composed of NH 3
and nitrogen by absorbing ammonia into a liquid solvent which is flowing downward in the absorption
unit (refer figure below). The gas stream flows upwards and is free of solvent. The downward flowing
liquid stream can contain ammonia and solvent but remains free of nitrogen. The weight fraction of NH 3
in the gas stream A leaving the process is related to the weight fraction of NH 3 in the liquid stream B
𝐴𝐴 𝐵𝐵
leaving the process by the following relation: 𝑥𝑥𝑁𝑁𝐻𝐻3
= 2𝑥𝑥𝑁𝑁𝐻𝐻3
Given the data shown in Figure-1:
a. Completely label the flow diagram and determine whether the given system is solvable or
not.
b. Calculate the flow rates (kg/h) and compositions of streams A and B.

Solution
Labeled flow diagram

𝑛𝑛𝑑𝑑𝑑𝑑 = 4(𝑚𝑚̇1 , 𝑚𝑚̇2 , 𝑥𝑥1𝐴𝐴 , 𝑥𝑥1𝐵𝐵 ) − 3 bal.(𝑁𝑁2 , 𝑁𝑁𝑁𝑁3 , 𝑆𝑆) − 1 rel.(𝑥𝑥1𝐴𝐴 = 2𝑥𝑥1𝐵𝐵 ) = 0 ⇒ solvable
Converting mol fraction to mass fraction in gas stream entering the unit:
Basis: 10 mol ⇒ 1 mol 𝑁𝑁𝑁𝑁3 & 9 mol 𝑁𝑁2
⇒ 1 × 17 g 𝑁𝑁𝑁𝑁3 & 9 × 28 g 𝑁𝑁2
⇒ 17 g 𝑁𝑁𝑁𝑁3 & 252 g 𝑁𝑁2 ⇒ Total = 269 g
 17 252
⇒ 𝑥𝑥 = = 0.0632; (1 − 𝑥𝑥) = = 0.9368
269 269
Applying balances:
Total: 2000 = 𝑚𝑚̇1 + 𝑚𝑚̇2
Solvent: 1000 = 𝑚𝑚̇2 (1 − 𝑥𝑥1𝐵𝐵 )
𝑁𝑁2 : 936.8 = 𝑚𝑚̇1 (1 − 𝑥𝑥1𝐴𝐴 )
𝑥𝑥1𝐴𝐴 = 2𝑥𝑥1𝐵𝐵
936.8 1000
⇒ 𝑚𝑚̇1 = ; 𝑚𝑚̇2 =
�1−2𝑥𝑥 1𝐵𝐵 � �1−𝑥𝑥 1𝐵𝐵 �
936.8 1000
⇒ 2000 = +
�1−2𝑥𝑥 1𝐵𝐵 � �1−𝑥𝑥 1𝐵𝐵 �
⇒ 4000(𝑥𝑥1𝐵𝐵 )2 − 3063.2𝑥𝑥1𝐵𝐵 + 63.2 = 0
⇒ 𝑥𝑥1𝐵𝐵 = 0.7446 & 0.0212
⇒ 𝑥𝑥1𝐵𝐵 = 0.0212 (𝑥𝑥1𝐵𝐵 = 0.7446 Cannot be the correct answer)
⇒ 𝑥𝑥1𝐴𝐴 = 0.0424
⇒ 𝑚𝑚̇1 = 977.25 kg ; 𝑚𝑚̇2 = 1021.7 kg
Problem-2: In the production of seed oil, the seeds are chopped and crushed, and these chopped and
crushed seeds are fed to a stirred vessel in which the seeds come in contact with a solvent (usually
hexane). Assume that all of the oil in seeds is extracted into the solvent hexane. The seeds contain 13 wt%
oil and 87% solids. The hexane to seed ratio in feed to the stirred vessel is 3 kg hexane/kg seeds. The
exits stream from the stirred vessel passes to a filtration unit. The liquid filtrate is sent to an evaporator
which vaporizes all the hexane and the oil is collected as liquid from the evaporator. The hexane vapors
from the evaporator are condensed to liquid hexane, and the liquid hexane is recycled back to join the
fresh stream of hexane. The filter cake from the filtration unit contains 75 wt% solids and balance seed oil
and hexane. The ratio of oil to hexane is same as in the stream entering into the filter unit. The filter cake
is discarded (and hence some solvent hexane is lost which is the reason we need to add fresh make up
hexane). The process is shown schematically in the figure given below.
a. Draw and complete the labeling of the flowchart.
b. Do the degree of freedom analysis for overall system and each of the single unit subsystems.
c. Assuming a basis of 100 kg/h (or kg) seed fed to the stirred vessel; calculate all unknowns in the
labeled flowchart and report the recycle ratio.

Solution:
Labeled flowchart:
Degree of freedom analysis:
Overall: 𝑛𝑛𝑑𝑑𝑑𝑑 = 4 unknowns (𝑚𝑚1 , 𝑚𝑚3 , 𝑦𝑦3 , 𝑚𝑚6 ) − 3 bal. = 1
Mixing point: 𝑛𝑛𝑑𝑑𝑑𝑑 = 2 (𝑚𝑚1 , 𝑚𝑚5 ) − 1 bal. = 1
Extractor: 𝑛𝑛𝑑𝑑𝑑𝑑 = 3 (𝑚𝑚2 , 𝑥𝑥2 , 𝑦𝑦2 ) − 3 bal. = 0
Filter: 𝑛𝑛𝑑𝑑𝑑𝑑 = 7 (𝑚𝑚2 , 𝑥𝑥2 , 𝑦𝑦2 , 𝑚𝑚3 , 𝑦𝑦3 , 𝑚𝑚4 , 𝑦𝑦4 ) − 3 bal. − 1 (𝑂𝑂𝑂𝑂𝑂𝑂 to 𝐻𝐻𝑒𝑒𝑒𝑒 ratio) = 3
Evaporator: 𝑛𝑛𝑑𝑑𝑑𝑑 = 4 (𝑚𝑚4 , 𝑦𝑦4 , 𝑚𝑚1 , 𝑚𝑚5 ) − 2 bal. = 2
⇒ Start with extractor
Material balance:
Extractor:
Total: 𝑚𝑚2 = 400 kg
Oil balance: 400𝑦𝑦2 = 13 ⇒ 𝑦𝑦2 = 0.0325 kg oil/kg
S balance: 400𝑥𝑥2 = 87 ⇒ 𝑥𝑥2 = 0.2175 kg S/kg
Filter:
S balance: 𝑚𝑚2 𝑥𝑥2 = 0.75𝑚𝑚3 ⇒ 𝑚𝑚3 = 116 kg
Total: 𝑚𝑚2 = 𝑚𝑚3 + 𝑚𝑚4 ⇒ 𝑚𝑚4 = 284 kg
𝑦𝑦2 𝑦𝑦3
Ratio: = ⇒ 𝑦𝑦3 = 0.0104 kg oil/kg
1−𝑥𝑥 2 −𝑦𝑦2 0.25−𝑦𝑦3
Oil balance: 𝑚𝑚2 𝑦𝑦2 = 𝑚𝑚3 𝑦𝑦3 + 𝑚𝑚4 𝑦𝑦4 ⇒ 𝑦𝑦4 = 0.0415 kg oil/kg
Evaporator:
Oil balance: 𝑚𝑚4 𝑦𝑦4 = 𝑚𝑚6 ⇒ 𝑚𝑚6 = 11.8 kg oil
Total: 𝑚𝑚4 = 𝑚𝑚6 + 𝑚𝑚5 ⇒ 𝑚𝑚5 = 272.2 kg 𝐻𝐻𝑒𝑒𝑒𝑒 (𝑣𝑣)
Mixing point: 300 = 𝑚𝑚1 + 𝑚𝑚5 ⇒ 𝑚𝑚1 = 27.8 kg 𝐻𝐻𝑒𝑒𝑒𝑒 (𝑙𝑙)
𝑚𝑚 5
Recycle ratio = = 9.79 kg 𝐻𝐻𝑒𝑒𝑥𝑥 recycled/kg 𝐻𝐻𝑒𝑒𝑒𝑒 fed
𝑚𝑚 1
Problem-3: A counter-current extraction process to recover benzene from a stream that contains 15wt.%
benzene and rest solids is shown in the following figure. The stream from which benzene is to be
extracted is fed to unit-2 at a flow rate of 2500 kg/h. The liquid organic solvent enters unit-1 at a flow rate
of 1500 kg/h. The mass fraction of the benzene in the solids stream (F) and the clear liquid stream (S)
1 2 2 1
have the following relations: 10 𝑤𝑤𝐵𝐵𝐹𝐹 = 𝑤𝑤𝐵𝐵𝑆𝑆 and 10 𝑤𝑤𝐵𝐵𝐹𝐹 = 𝑤𝑤𝐵𝐵𝑆𝑆
Determine the benzene and solvent concentrations in all of the streams, and solve for all unknown
variables. Before solving for unknown variables, show that the system is solvabe.

Solution: Labeled flowchart

DOF analysis:
Unit-1:
1 1 2
𝐷𝐷𝐷𝐷𝐷𝐷 = 6�𝑆𝑆 1 , 𝐹𝐹1 , 𝐹𝐹 2 , 𝑤𝑤𝐵𝐵𝐹𝐹 , 𝑤𝑤𝐵𝐵𝑆𝑆 , 𝑤𝑤𝐵𝐵𝐹𝐹 � − 3 𝑀𝑀𝑀𝑀𝑀𝑀. 𝐵𝐵𝐵𝐵𝐵𝐵. (𝐵𝐵, 𝑆𝑆𝑆𝑆𝑆𝑆, 𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠) − 1𝑟𝑟𝑟𝑟𝑙𝑙 𝑛𝑛 = 2
Unit-2
1 1 2
𝐷𝐷𝐷𝐷𝐷𝐷 = 6�𝑆𝑆 1 , 𝐹𝐹1 , 𝑆𝑆 2 , 𝑤𝑤𝐵𝐵𝐹𝐹 , 𝑤𝑤𝐵𝐵𝑆𝑆 , 𝑤𝑤𝐵𝐵𝑆𝑆 � − 3 𝑀𝑀𝑀𝑀𝑀𝑀. 𝐵𝐵𝐵𝐵𝐵𝐵. (𝐵𝐵, 𝑆𝑆𝑆𝑆𝑆𝑆, 𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠) − 1𝑟𝑟𝑟𝑟𝑙𝑙 𝑛𝑛 = 2
Overall:
2 2
𝐷𝐷𝐷𝐷𝐷𝐷 = 4�𝑆𝑆 2 , 𝐹𝐹 2 , 𝑤𝑤𝐵𝐵𝑆𝑆 , 𝑤𝑤𝐵𝐵𝐹𝐹 � − 3 𝑀𝑀𝑀𝑀𝑀𝑀. 𝐵𝐵𝐵𝐵𝐵𝐵. (𝐵𝐵, 𝑆𝑆𝑆𝑆𝑆𝑆, 𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠) = 1
Thus, we must now check for DOF of the process.
1 2 1 2
𝐷𝐷𝐷𝐷𝐷𝐷 = 8�𝑆𝑆 1 , 𝑆𝑆 2 , 𝐹𝐹1 , 𝐹𝐹 2 , 𝑤𝑤𝐵𝐵𝑆𝑆 , 𝑤𝑤𝐵𝐵𝑆𝑆 , 𝑤𝑤𝐵𝐵𝐹𝐹 , 𝑤𝑤𝐵𝐵𝐹𝐹 � − 3 𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏 𝑜𝑜𝑜𝑜 𝑢𝑢𝑢𝑢𝑢𝑢𝑢𝑢 − 3 𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏 𝑜𝑜𝑜𝑜 𝑢𝑢𝑢𝑢𝑢𝑢𝑢𝑢 − 2
− 2𝑟𝑟𝑟𝑟𝑙𝑙 𝑛𝑛 = 0
Thus, system is solvable.
Applying material balances:
Solid balance on unit-1:
𝐹𝐹 0 × 0.85 = 𝐹𝐹1 × 0.9 ⇒ 𝐹𝐹1 = 2361.1 kg/h
Solid balance on unit-2:
𝐹𝐹1 × 0.9 = 𝐹𝐹 2 × 0.9 ⇒ 𝐹𝐹 2 = 2361.1 kg/h
Total balance on unit-1:
𝐹𝐹1 + 1500 = 𝑆𝑆 1 + 𝐹𝐹 2 ⇒ 𝑆𝑆 1 = 1500 kg/h
Total balance on unit-2:
𝑆𝑆 1 + 2500 = 𝑆𝑆 2 + 𝐹𝐹1 ⇒ 𝑆𝑆 2 = 1638.9 kg/h
Benzene balance on unit-1
 2 1 1
𝐹𝐹 2 𝑤𝑤𝐵𝐵𝐹𝐹 + 𝑆𝑆 1 𝑤𝑤𝐵𝐵𝑆𝑆 = 𝐹𝐹1 𝑤𝑤𝐵𝐵𝐹𝐹
2 2 1
2361.1 𝑤𝑤𝐵𝐵𝐹𝐹 + 1500�10𝑤𝑤𝐵𝐵𝐹𝐹 � = 2361.1 𝑤𝑤𝐵𝐵𝐹𝐹
2 1
𝑤𝑤𝐵𝐵𝐹𝐹 = 0.136𝑤𝑤𝐵𝐵𝐹𝐹
Benzene balance on unit-2:
1 2 1
2500 × 0.15 + 1500𝑤𝑤𝐵𝐵𝑆𝑆 = 𝑆𝑆 2 𝑤𝑤𝐵𝐵𝑆𝑆 + 𝐹𝐹1 𝑤𝑤𝐵𝐵𝐹𝐹
2 1 1
2500 × 0.15 + 1500(10𝑤𝑤𝐵𝐵𝐹𝐹 ) = 𝑆𝑆 2 (10𝑤𝑤𝐵𝐵𝐹𝐹 ) + 𝐹𝐹1 𝑤𝑤𝐵𝐵𝐹𝐹
1
𝑤𝑤𝐵𝐵𝐹𝐹 = 0.0224
2 2 1
𝑤𝑤𝐵𝐵𝑆𝑆 = 0.224; 𝑤𝑤𝐵𝐵𝐹𝐹 = 0.00305; 𝑤𝑤𝐵𝐵𝑆𝑆 = 0.0305
 Material Balance Fundamentals- Reactive Systems
Stoichiometry and Terminology for Reactive Systems)

Consider the following balanced chemical reaction equation (or Stoichiometric equation):

C7 H16 (l) + 11O2 (g) → 7CO2 (g) + 8H2 O (g)

The number that precedes the chemical formula for each species is known as stoichiometric coefficient.
The stoichiometric equation gives information about the molar ratio in which different chemical species
(reactants or products) are taking part in that particular reaction. For example, in the second equation
written above for combustion of heptane, 1 mole of heptane combines with 11 moles of oxygen to
produce 7 moles of CO2 and 8 moles of water. One can define stoichiometric ratios such as: 11 mol O2
consumed/1 mol C7H16 consumed or 11 kmol (or lb-mol) O2 consumed/7 kmol (or lb-mol) CO2 produced
etc.

A general chemical stoichiometric equation can be written as: ∑𝑁𝑁 𝑖𝑖=1 𝜈𝜈𝑖𝑖 𝑆𝑆𝑖𝑖 ≡ 0 , where 𝜈𝜈𝑖𝑖 is the
stoichiometric coefficient and 𝑆𝑆𝑖𝑖 is the i chemical species. The stoichiometric coefficient is taken as
th

positive if i is product species and negative if i is reactant species. Accordingly, for combustion reaction
of heptane given above: 𝜈𝜈𝐶𝐶7𝐻𝐻16 = −1, 𝜈𝜈𝑂𝑂2 = −11, 𝜈𝜈𝐶𝐶𝐶𝐶2 = 7, 𝜈𝜈𝐻𝐻2𝑂𝑂 = 8.

It is more often the case that the reactants are not present in stoichiometric amounts and the reaction
rarely goes to completion in real situations. We define several terms to account for incomplete reaction
and presence of reactants in non-stoichiometric proportions.

Extent of reaction: is calculated by taking the ratio of change in number of moles of specie that occur in
a reaction (i.e. reactant or product species) to the corresponding stoichiometric coefficient. For general
chemical reaction ∑𝑁𝑁𝑖𝑖=1 𝜗𝜗𝑖𝑖 𝑆𝑆𝑖𝑖 ≡ 0, extent of reaction

amount consumed or generated 𝑛𝑛𝑖𝑖 − 𝑛𝑛𝑖𝑖0

ζ = =
𝜈𝜈𝑖𝑖 𝜈𝜈𝑖𝑖

Thus 𝑛𝑛𝑖𝑖 = 𝑛𝑛𝑖𝑖0 + 𝜈𝜈𝑖𝑖 ζ.

For continuous processes, number of moles will be replaced by molar flow-rates. Note that 𝑛𝑛𝑖𝑖 − 𝑛𝑛𝑖𝑖0 =
𝜈𝜈𝑖𝑖 ζ = amount consumed or generated. This implies that if several independent reactions occur in a
reactor, extent of reaction will be defined for each independent reaction. The final amount of specie i then
would be given by adding the amount generated (for product species) or consumed (for reactant species)
for ith species in each of the independent reactions. Thus, the relation between initial and final number of
moles for ith species for the case of 'R' independent reactions will be given as:
𝑅𝑅

𝑛𝑛𝑖𝑖 = 𝑛𝑛𝑖𝑖0 + � 𝜈𝜈𝑖𝑖 ζ𝑘𝑘

𝑘𝑘=1

Limiting and Excess Reactants: Consider the following reaction:

C7 H16 (l) + 11O2 (g) → 7CO2 (g) + 8H2 O (g)

If the reactants are fed in stoichiometric ratio, for example, 10 mol of heptane and 110 mol of oxygen and
reaction proceeds to completion, then, at the end of reaction, no heptane or oxygen will be left. However,
if we start with 10 mol of heptane and 100 mol of oxygen, oxygen will finish out first. The reactant which
will theoretically run out first (i.e. assuming complete reaction) is called as limiting reactant. All other
reactants are termed as excess reactants. Note that it is not necessary that reaction goes to completion in
practice; the limiting reactant is identified assuming complete reaction. For excess reactants, we define
fractional excess as:

(𝑛𝑛𝑖𝑖 )𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓 − (𝑛𝑛𝑖𝑖 )𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠 ℎ

fraction excess of 𝑖𝑖 𝑡𝑡ℎ species =
(𝑛𝑛𝑖𝑖 )𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠 ℎ

where, (𝑛𝑛𝑖𝑖 )𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓 and (𝑛𝑛𝑖𝑖 )𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠 ℎ are number of moles of ith species in feed and number of moles required as
per stoichiometric equation.

Note:

1. Limiting reactant can be determined either by (i) comparing the feed mole to stoichiometric mole
ratio for all reactants or by (ii) finding out maximum extent of reaction assuming complete
conversion of each reactant. The reactant with smallest extent of reaction is the limiting reactant.
Both the approaches are shown in one of the unit level problem.
2. The concept of limiting reaction is valid only for single reaction and do not hold for multiple
reactions occurring simultaneously.

moles reacted (𝑛𝑛 𝑖𝑖0 − 𝑛𝑛 𝑖𝑖 )

Fractional Conversion: 𝑓𝑓 = =
moles fed 𝑛𝑛 𝑖𝑖0

Yield and Selectivity for multiple reactions: Consider the production of ethylene by dehydrogenation of
ethane:

C2H6 → C2H4 + H2 Desired reaction (1)

Once, some hydrogen is produced, two side reactions can also occur which consume reactant (C2H6) and
produce undesired products (CH4 and C3H6).

C2H6 + H2 → 2 CH4 Undesired reaction (2)

C2H6 + C2H4 → C3H6 + CH4 Undesired reaction (3)

Since the objective of the process was to produce ethylene (C2H4), only reaction (1) is desirable and other
two reactions (i.e. (2) and (3)) are undesirable. While designing reactor for the production of ethylene
from ethane, the design engineer not only considers maximization of desired product (ethylene in this
case) but also strategies on how to minimize undesired products. Two terms yield and selectivity are used
to quantify the degree of occurrence of desired reaction over undesired reactions.

moles of desired product formed

Yield = moles that would have been formed if there were no side
reactions and the limiting reactant had reacted completely
moles of desired product formed
Selectivity =
moles of undesired product formed
Problem-1: Consider combustion of heptane in a combustion chamber: C7 H16 (l) + 11O2 (g) →
7CO2 (g) + 8H2 O (g). 5 mol of heptane and 50 mol of O2 are fed in the combustion chamber. After
sometime, 2mol of heptane reacts, calculate extent of reaction at this instant of time.

Solution: C7 H16 (l) + 11O2 (g) → 7CO2 (g) + 8H2 O (g)

Initially: 𝑛𝑛𝑖𝑖𝑖𝑖 5 mol 50 mol 0 mol 0 mol

Final: 𝑛𝑛𝑖𝑖 2 mol 17 mol 21 mol 24 mol

𝑛𝑛𝑖𝑖 − 𝑛𝑛𝑖𝑖𝑖𝑖 2 − 5
𝜁𝜁 = = =3
𝜈𝜈𝑖𝑖 −1

Note that 𝜁𝜁 will be 3 whether the calculations are done based on number of moles of any species (verify
it).
Problem-2: Consider production of acrylonitrile from the reaction of propylene, ammonia, and oxygen:
C3H6 + NH3 + 1.5 O2 → C3H3N + 3 H2O. The feed consists of 10 mol% propylene, 12% ammonia, and
balance air. Identify the limiting reactant and fractional excess of other reactants.

Solution:

Assume a basis of 100 mol of feed ⇒ 10 mol propylene, 12 mol ammonia and 78 mol air (= 16.38 mol O2
and 61.62 mol N2).
𝑛𝑛 𝑖𝑖 −𝑛𝑛 𝑖𝑖𝑖𝑖
Identification of limiting reactant using extent of reaction: 𝜁𝜁 = , with 𝑛𝑛𝑖𝑖 = 0 to calculate maximum
𝜈𝜈 𝑖𝑖
extent of reaction.

0 − 10
𝜁𝜁 𝑚𝑚𝑚𝑚𝑚𝑚 (𝐶𝐶3 𝐻𝐻6 ) = = 10
−1
0 − 12
𝜁𝜁 𝑚𝑚𝑚𝑚𝑚𝑚 (𝑁𝑁𝐻𝐻3 ) = = 12
−1
0 − 16.38
𝜁𝜁 𝑚𝑚𝑚𝑚𝑚𝑚 (𝑂𝑂2 ) = = 10.92
−1.5

Thus, 𝜁𝜁 max has minimum value for C3H6 and hence, propylene is the limiting reactant and ammonia and
oxygen are excess reactants.

Identification of limiting reactant by comparing ratio:

𝐶𝐶3 𝐻𝐻6 10 𝐶𝐶3 𝐻𝐻6 1

� � = < � � = ⇒ propylene is limiting with respect to ammonia
𝑁𝑁𝐻𝐻3 𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓 12 𝑁𝑁𝐻𝐻3 𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠 ℎ 1

(because propylene is present in lesser amount in feed than stoichiometric requirement, 12 mol of
ammonia requires 12 mol of propylene as per stoichiometric equation)

𝑂𝑂2 16.38 𝑂𝑂2

� � = = 1.365 < � � = 1.5 ⇒ oxygen is limiting w.r.t to ammonia
𝑁𝑁𝐻𝐻3 𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓 12 𝑁𝑁𝐻𝐻3 𝑠𝑠𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡 ℎ

𝐶𝐶3 𝐻𝐻6 10 𝐶𝐶3 𝐻𝐻6 1

� � = = 0.61 < � � = = 0.666 ⇒ propylene is limiting w.r.t to oxygen
𝑂𝑂2 𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓 16.38 𝑂𝑂2 𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠 ℎ 1.5

Thus, comparing the above ratios, propylene is limiting reactant.

�𝑛𝑛𝑁𝑁𝐻𝐻3 � − �𝑛𝑛𝑁𝑁𝐻𝐻3 � 12 − 10
𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓 𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠 ℎ
(% excess)𝑁𝑁𝐻𝐻3 = 100 � � = 100 � � = 20%
�𝑛𝑛𝑁𝑁𝐻𝐻3 � 10
𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠

Similarly,

�𝑛𝑛𝑂𝑂2 � − �𝑛𝑛𝑂𝑂2 � 0.21 × 78 − 1.5 × 10

𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓 𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠 ℎ
(% excess)𝑂𝑂2 = 100 � � = 100 � � = 9.20%
�𝑛𝑛𝑂𝑂2 � 10 × 1.5
𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠
Problem-3: The following reaction takes place in a continuous reactor: A + B + 3 C → D + 3 E. The feed
contains 15 mol% A, 10% B and 75% C. A fractional conversion of 0.4 of the limiting reactant is
achieved in the reactor. Assuming 100 mol/h of feed, determine the composition of product stream exiting
the reactor.

Solution: The flowchart of the process is shown in Figure

Since, the conversion of limiting reactant is given, we first require to identify the limiting reactant.

𝑛𝑛𝑖𝑖 (= 0) − 𝑛𝑛𝑖𝑖𝑖𝑖 𝑛𝑛𝑖𝑖𝑖𝑖

𝜁𝜁𝑖𝑖 max = =−
𝜈𝜈𝑖𝑖 𝑣𝑣𝑖𝑖

0 − 15
𝜁𝜁 𝑚𝑚𝑚𝑚𝑚𝑚 (𝐴𝐴) = = 15
−1
0 − 10
𝜁𝜁 𝑚𝑚𝑚𝑚𝑚𝑚 (𝐵𝐵) = = 10
−1
0 − 75
𝜁𝜁 𝑚𝑚𝑚𝑚𝑚𝑚 (𝐶𝐶) = = 45
−3

Thus, 𝜁𝜁 max is minimum for B and hence, B is limiting reactant. Thus we are given 40% conversion for B
⇒ 𝑓𝑓B = 0.4 ⇒ 𝑛𝑛B = 𝑛𝑛B0 (1 − f) = 10(1 − 0.4) = 6 mol B

𝑛𝑛B = 𝑛𝑛B0 + 𝜈𝜈B 𝜁𝜁 ⇒ 𝜁𝜁 = 4 mol

Thus,

𝑛𝑛A = 𝑛𝑛A0 + 𝜈𝜈𝐴𝐴 𝜁𝜁 = 15 − 1 × 𝜁𝜁 = 11 mol A

𝑛𝑛C = 𝑛𝑛C0 + 𝜈𝜈C 𝜁𝜁 = 75 − 3 × 𝜁𝜁 = 63 mol C

𝑛𝑛D = 𝑛𝑛D0 + 𝜈𝜈𝐷𝐷 𝜁𝜁 = 0 + 1 × 𝜁𝜁 = 4 mol D

𝑛𝑛E = 𝑛𝑛E0 + 𝜈𝜈E 𝜁𝜁 = 0 + 3 × 𝜁𝜁 = 12 mol E

Problem-4: Formaldehyde (HCHO) is produced by reacting methane with oxygen over a particular
catalyst (CH4 + O2 →HCHO + H2O). One side reaction also occurs along with the desired reaction giving
carbon dioxide as undesired product (CH4 + 2 O2 → CO2 + 2 H2O). The feed to the reactor is 10 mol/h
methane, and 100 mol/h air. A fractional conversion of 60% of methane is obtained in the reactor and
yield of formaldehyde is 0.45. Calculate the amounts of all species leaving the reactor and selectivity of
formaldehyde to carbon dioxide production.

Solution: CH4 + O2 →HCHO + H2O (Desired reaction)

CH4 + 2 O2 → CO2 + 2 H2O (Undesired reaction)

The flowchart is shown in Figure

Given 𝑓𝑓CH4 = 0.4,

𝑛𝑛CH4 = (1 − 0.6)10 = 4 mol CH4 /h

𝑛𝑛𝐻𝐻𝐻𝐻𝐻𝐻𝐻𝐻
Yield =
moles that would have been formed in absence of side reaction
and complete conversion of limiting reactant
𝑛𝑛HCHO
0.45 = ⇒ 𝑛𝑛HCHO = 4.5 mol HCHO/h
10

𝑛𝑛HCHO = 0 + ζ1 ⇒ ζ1 = 4.5 mol/h

𝑛𝑛CH4 = 4 = 10 − ζ1 − ζ2 ⇒ ζ2 = 1.5 mol/ℎ

𝑛𝑛O2 = 21 − ζ1 − 2 ζ2 = 21 − 4.5 − 2 × 1.5 = 13.5 mol Oxygen/h

𝑛𝑛𝐶𝐶𝑂𝑂2 = 𝜁𝜁2 = 1.5 molCO2 /h

𝑛𝑛H2 O = 0 + 𝜁𝜁1 + 2𝜁𝜁2 = 7.5 mol H2 O/h

moles desired 4.5 mol HCHO

selectivity = = =3
moles undesired 1.5 mol CO2
 Material Balance Fundamentals- Reactive Systems
(Approaches for Balances on Reactive Systems)

Consider a simple single unit reactive process where ethane undergoes dehydrogenation to give ethylene
and hydrogen (C2 H6 → C2 H4 + H2 ).

Figure 3.2.1

In the above process, three chemical species are involved (C2H6, C2H4, and H2) and two atomic species
are present (C and H).We can write down balances on chemical species, or atomic species for the above
process. Recall, the steady state material balance equation for a reactive system is:

input + generation = output + consumption

While using chemical species balance, one can in principle, use mole or mass balance, however, mole
balance is a preferred choice because one can directly relate the balance with stoichiometric equation.
Note that, if we use atomic species balance, the generation and consumption terms will vanish from the
balance equation (except for nuclear reaction which we will not be considering in this course). Thus, for
steady state process, the atomic species balance will be simply: input = output.

Thus, we can use either a chemical species balance or atomic species balance for solving unknowns in a
reactive process. Accordingly, we say that we use two different approaches: (i) extent of reaction
approach, where we are primarily using chemical species balance, and (ii) atomic species balance
approach (with balance equation input = output). We use the above flowchart/process (Figure 3.2.1) to
illustrate both the approaches. The steps discussed in context of non-reactive processes will remain
exactly identical i.e. choosing a basis, drawing of flowchart, DOF analysis and finally, writing material
balance equations. The calculation of DOF and balance equation will be different in the two approaches
as illustrated in the following discussion.
𝑅𝑅

𝑛𝑛𝑖𝑖 = 𝑛𝑛𝑖𝑖𝑖𝑖 + � 𝜈𝜈𝑖𝑖𝑖𝑖 𝜁𝜁𝑘𝑘

𝑘𝑘=1

Extent of Reaction Approach: Balances on each reactive species are used to generate independent
equations. The steady state balance equation for a chemical species is:
input + generation = output + consumption. Using the definition of extent of reaction (𝜁𝜁), this balance
can be written for species "i" in terms of number of moles leaving (𝑛𝑛𝑖𝑖 ) and entering the system (𝑛𝑛𝑖𝑖𝑖𝑖 ) as:
 𝑅𝑅

𝑛𝑛𝑖𝑖 = 𝑛𝑛𝑖𝑖𝑖𝑖 + � 𝜈𝜈𝑖𝑖𝑖𝑖 𝜁𝜁𝑘𝑘

𝑘𝑘=1

Note that (𝑛𝑛𝑖𝑖 − 𝑛𝑛𝑖𝑖𝑖𝑖 ) represents output minus input and term (𝜈𝜈𝑖𝑖𝑖𝑖 𝜁𝜁𝑘𝑘 ) represents the consumption (if i is
reactant) or generation (if i is product species) of ith species via kth reaction. Summation over all such
terms then gives total generation or consumption of species i in the process. The DOF is calculated as:

DOF = No. of unknown labeled variables + No. of independent reactions (one extent of reaction for each
reaction) - No. of independent reactive species (one 𝑛𝑛𝑖𝑖 expression for each species) - No. of independent
non-reactive species - No. of equations relating unknown variables (process specifications etc.)

Thus, considering the above flowchart:

DOF = 2 (𝑛𝑛1 , 𝑛𝑛2 ) + 1 independent reaction - 3 reactive species (𝑛𝑛𝑖𝑖 expressions for C2H6, C2H4, H2) = 0

kmol
𝑛𝑛H 2 = �𝑛𝑛H 2 � + 𝜁𝜁 ⇒ 40 = 0 + 𝜁𝜁 ⇒ 𝜁𝜁 = 40
0 min
kmol
𝑛𝑛𝐶𝐶2 𝐻𝐻6 = �𝑛𝑛𝐶𝐶2 𝐻𝐻6 � − 𝜁𝜁 = 100 − 40 = 60
0 min
kmol
𝑛𝑛𝐶𝐶2𝐻𝐻 4 = �𝑛𝑛𝐶𝐶2𝐻𝐻 4 � + 𝜁𝜁 = 0 + 40 = 40
0 min

Atomic Species Balance Approach: Balance will be of the form input = output.

DOF = No. of unknown labeled variables - No. of independent atomic species balance - No. of
independent non-reactive species - No. of equations relating unknown variables (process specifications
etc.).

For the above example of dehydrogenation of ethane:

DOF = 2 unknowns (𝑛𝑛1 , 𝑛𝑛2 ) - 2 independent atomic species balance (C & H) - 0 relation or inert species
balance = 0 ⇒ solvable ⇒ write C and H balance to find unknowns.

C- Balance:

input = output

kmol ethane
2 𝑛𝑛1 + 2 𝑛𝑛2 = 100 × 2 = 200
min
H - Balance:

6 × 100 = 40 × 2 + 6 𝑛𝑛1 + 4 𝑛𝑛2

Solving the above two equations yield 𝑛𝑛1 and𝑛𝑛2 .

Note:

• Atomic species balance usually leads to a more straight-forward solution procedure particularly
when more than one reaction is involved.
• Extent of reaction approach is convenient for chemical equilibrium problems.
• Recall the ratio rule we discussed in context of balances on non-reactive systems. We repeat it
here: If two species (non-reactive) are present in the same ratio wherever they occur in the
process, then balances on these two species will not be independent and we will have only one
independent balance. Similar principle applies for atomic species balance for a reactive system.
Let us understand this with a simple example. For the flow sheet shown in Figure 3.2.1, three
independent species balance can be written (H2, C2H4, and C2H6) and two independent atomic
balances can be written (C and H). However, for the process shown below (Figure 3.2.2), three
independent chemical species balance exist while only two independent atomic species balances
are possible (C or H and N) out of three atomic species present in the system (C, H, and N). Note
that the reaction stoichiometry and feed stream is such that the ratio of C/H is identical in both
input and output streams.

Figure 3.2.2

Independent reactions and Independent element balance:

The calculation of DOF in extent of reaction approach requires the determination of number of
independent reactions. We describe the determination of number of independent reactions out of a given
set of reactions by considering the following reactions:

𝐶𝐶𝐻𝐻4 + 𝐶𝐶𝑂𝑂2 → 2 𝐶𝐶𝐶𝐶 + 2 𝐻𝐻2 (1)

𝐶𝐶𝐶𝐶 + 𝐻𝐻2 𝑂𝑂 → 𝐶𝐶𝑂𝑂2 + 𝐻𝐻2 (2)
𝐶𝐶𝐻𝐻4 + 𝐻𝐻2 𝑂𝑂 → 𝐶𝐶𝐶𝐶 + 3 𝐻𝐻2 𝑂𝑂 (3)
𝐶𝐶𝐻𝐻4 + 2 𝐻𝐻2 𝑂𝑂 → 𝐶𝐶𝑂𝑂2 + 4 𝐻𝐻2 (4)
We form a specie matrix as shown below:

reaction 𝐶𝐶𝐻𝐻4 𝐶𝐶𝑂𝑂2 𝐶𝐶𝐶𝐶 𝐻𝐻2 𝐻𝐻2 𝑂𝑂

(1) ⎡ −1 −1 2 2 0 ⎤
(2) ⎢ ⎥
⎢ 0 1 −1 1 −1 ⎥
(3) ⎢ −1 0 1 3 −1 ⎥
(4) ⎣ −1 1 0 4 −2 ⎦

The rank of this matrix will be equal to the number of independent reactions out of the given reactions.
For above matrix, the rank = 2 ⇒only two reactions are independent out of given four reactions.
In a similar fashion, the atomic species balance approach requires the determination of independent
atomic species. The number of independent atomic species balance can be determined as follows.
Consider we are given a process which involves two reactions: CO + 2 H2 → CH3OH and CO + 3 H2 →
CH4 + H2O. Thus, the process involves three elements (C, H, and O) and five species (CO, H2, CH3OH,
CH4, and H2O). We prepare a matrix in which rows are elements or atomic species and columns are
species involved in the process. The rank of such a matrix is equal to the number of independent atomic
species balances. The resulting matrix is:

element 𝐻𝐻2 𝐻𝐻2 𝑂𝑂 𝐶𝐶𝐶𝐶 𝐶𝐶𝐻𝐻4 𝐶𝐶𝐻𝐻3 𝑂𝑂𝑂𝑂

𝐻𝐻 2 2 0 4 4
� �
𝑂𝑂 0 1 1 0 1
𝐶𝐶 0 0 1 1 1

The rank of the above matrix is 3 and hence all three elemental balances are independent. On the other
hand, if we consider the reaction: H2O + SO3 → H2SO4 and prepare the matrix as given below:

element 𝐻𝐻2 𝑂𝑂 𝑆𝑆𝑂𝑂3 𝐻𝐻2 𝑆𝑆𝑂𝑂4

𝐻𝐻 2 0 2
� �
𝑆𝑆 0 1 1
𝑂𝑂 1 3 4

Rank of this matrix is two ⇒only two balances (H and S or O) out of three (H, S, and O) are independent.
Note that in order to determine rank, we express the matrix in row-echelon form by performing
𝑅𝑅1
elementary row-operations: 𝑅𝑅1 → ;𝑅𝑅3 → 𝑅𝑅3 − 𝑅𝑅1 ;𝑅𝑅3 → 𝑅𝑅3 − 3 𝑅𝑅2 .These three operations are shown
2
below:

element 𝐻𝐻2 𝑂𝑂 𝑆𝑆𝑂𝑂3 𝐻𝐻2 𝑆𝑆𝑂𝑂4

𝐻𝐻 1 0 1
� �
𝑆𝑆 0 1 1
𝑂𝑂 1 3 4
element 𝐻𝐻2 𝑂𝑂 𝑆𝑆𝑂𝑂3 𝐻𝐻2 𝑆𝑆𝑂𝑂4
𝐻𝐻 1 0 1
� �
𝑆𝑆 0 1 1
𝑂𝑂 0 3 3
element 𝐻𝐻2 𝑂𝑂 𝑆𝑆𝑂𝑂3 𝐻𝐻2 𝑆𝑆𝑂𝑂4
𝐻𝐻 1 0 1
� �
𝑆𝑆 0 1 1
𝑂𝑂 0 0 0

The last matrix is in row-echelon form. Note that in 2nd matrix (or after 2nd row-operation), Row-2 and
Row-3 are multiple of each other and correspond to the number of S and O in different chemical species
taking part in the process. This implies that the ratio of S and O is identical in the process and hence, only
one balance out of the two (S and O) will be independent balance.
Problem-1: Formaldehyde is produced in reaction of methane with oxygen in presence of a catalyst.
Some amount of methane is also oxidized to carbon dioxide, carbon monoxide and water:

𝐶𝐶𝐻𝐻4 + 𝑂𝑂2 → 𝐻𝐻𝐻𝐻𝐻𝐻𝐻𝐻 + 𝐻𝐻2 𝑂𝑂

𝐶𝐶𝐻𝐻4 + 2 𝑂𝑂2 → 𝐶𝐶𝑂𝑂2 + 2 𝐻𝐻2 𝑂𝑂

3
𝐶𝐶𝐻𝐻4 + 𝑂𝑂 → 𝐶𝐶𝐶𝐶 + 2 𝐻𝐻2 𝑂𝑂
2 2
The feed to the reactor consists of equimolar mixture of methane and oxygen, and the feed flow-rate is
200 mol/h.

a) Draw and label a flowchart. Using extent of reaction approach, determine how many process
variables must be specified to calculate all unknowns in labeled flowchart.
b) Write down material balance equation using extent of reaction approach i.e. the expression of 𝑛𝑛𝑖𝑖
in terms of extent of reactions for each species taking part in the process.
c) Calculate all the unknowns if fractional conversion of methane is 0.9, yield of HCHO is 0.85,
and 5 mol CO2 is produced per mol of CO generated.

Solution:

(a) Basis of calculation is 200 mol/h of feed and flowchart is shown in Figure

Since, each of the reaction contains a new species, this implies that all three reactions are independent and
hence, we will have three extent of reaction for these three reactions.

DOF = 9 (𝑛𝑛1 to𝑛𝑛6 , 𝜁𝜁1 , 𝜁𝜁2 , 𝜁𝜁3 ) − 6 (𝑛𝑛𝑖𝑖 expression for 𝐶𝐶𝐻𝐻4 , 𝑂𝑂2 , 𝐻𝐻𝐻𝐻𝐻𝐻𝐻𝐻, 𝐻𝐻2 𝑂𝑂, 𝐶𝐶𝑂𝑂2 , 𝐶𝐶𝐶𝐶) = 3 ⇒3 process
variables or process specifications must be mentioned to solve for all unknowns.

(b)

𝑛𝑛1 = �𝑛𝑛𝐶𝐶𝐻𝐻4 � − 𝜁𝜁1 − 𝜁𝜁2 − 𝜁𝜁3 (1)

0
𝑛𝑛2 = �𝑛𝑛𝑂𝑂2 � − 𝜁𝜁1 − 2 𝜁𝜁2 − 1.5 𝜁𝜁3 (2)
0
𝑛𝑛3 = (𝑛𝑛𝐻𝐻𝐻𝐻𝐻𝐻𝐻𝐻 )0 + 𝜁𝜁1 (3)
𝑛𝑛4 = �𝑛𝑛𝐻𝐻2 𝑂𝑂 � + 𝜁𝜁1 + 2 𝜁𝜁2 + 2 𝜁𝜁3 (4)
0
𝑛𝑛5 = �𝑛𝑛𝐶𝐶𝑂𝑂2 � + 𝜁𝜁2 (5)
0
 𝑛𝑛6 = (𝑛𝑛𝐶𝐶𝐶𝐶 )0 + 𝜁𝜁3 (6)
mol
�𝑛𝑛𝐶𝐶𝐻𝐻4 �0 = �𝑛𝑛𝑂𝑂 2 � = 100 ; (𝑛𝑛𝐻𝐻𝐻𝐻𝐻𝐻𝐻𝐻 )0 = �𝑛𝑛𝐻𝐻2 𝑂𝑂 � = �𝑛𝑛𝐶𝐶𝑂𝑂2 � = (𝑛𝑛𝐶𝐶𝐶𝐶 )0 = 0 (7)
0 h 0 0

(c)

mol 𝐶𝐶𝐻𝐻4
𝑓𝑓𝐶𝐶𝐻𝐻4 = 0.9 ⇒ 𝑛𝑛1 = �1 − 𝑓𝑓𝐶𝐶𝐻𝐻4 ��𝑛𝑛𝐶𝐶𝐻𝐻4 � = (1 − 0.9) 100 = 10
0 h
moles of HCHO formed
Yield =
moles that would have been formed if there
were no side reactions and
limiting reactant is copletely consumed

𝑛𝑛3 mol 𝐻𝐻𝐻𝐻𝐻𝐻𝐻𝐻

Yield = 0.85 = ⇒ 𝑛𝑛3 = 85
100 h

𝑛𝑛5 = 5 𝑛𝑛6 (8)

mol
Using (3) and (7) 𝜁𝜁1 = 85
h

Using (6), (7), and (8):

𝜁𝜁2 = 5 𝜁𝜁3

Using the above relation and (1)

mol
𝜁𝜁3 = 0.8333
h
Thus, using expression of ni :

mol CO mol𝐶𝐶𝑂𝑂2 mol 𝑂𝑂2 mol H2 O

𝑛𝑛6 = 0.8333 ; 𝑛𝑛5 = 4.1667 ; 𝑛𝑛2 = 5.4105 ; n4 = 95
h h h h
Problem-2: We are required to solve the same problem as above by following atomic species balance
approach. For the sake of convenience the same problem is repeated here.

Formaldehyde is produced in reaction of methane with oxygen in presence of a catalyst. Some amount of
methane is also oxidized to carbon dioxide, carbon monoxide and water:

𝐶𝐶𝐻𝐻4 + 𝑂𝑂2 → 𝐻𝐻𝐻𝐻𝐻𝐻𝐻𝐻 + 𝐻𝐻2 𝑂𝑂

𝐶𝐶𝐻𝐻4 + 2 𝑂𝑂2 → 𝐶𝐶𝑂𝑂2 + 2 𝐻𝐻2 𝑂𝑂

3
𝐶𝐶𝐻𝐻4 + 𝑂𝑂 → 𝐶𝐶𝐶𝐶 + 2 𝐻𝐻2 𝑂𝑂
2 2
The feed to the reactor consists of equimolar mixture of methane and oxygen, and the feed flow-rate is
200 mol/h.

a) Draw and label a flowchart. Using atomic species or elemental balance approach, determine how
many process variables must be specified to calculate all unknowns in labeled flowchart.
b) Calculate all the unknowns if fractional conversion of methane is 0.9, yield of HCHO is 0.85,
and 5 mol CO2 is produced per mol of CO generated.

Solution:

(a) Basis of calculation is 200 mol/h of feed and flowchart is shown in Figure

Since, each of the reaction contains a new species, this implies that all three reactions are independent and
hence, we will have three extent of reaction for these three reactions.

DOF = 6 (𝑛𝑛1 to𝑛𝑛6 ) − 3 (C, H, O balances) = 3 ⇒3 process variables or process specifications must be
mentioned to solve for all unknowns.

(b)

mol 𝐶𝐶𝐻𝐻4
𝑓𝑓𝐶𝐶𝐻𝐻4 = 0.9 ⇒ 𝑛𝑛1 = �1 − 𝑓𝑓𝐶𝐶𝐻𝐻4 ��𝑛𝑛𝐶𝐶𝐻𝐻4 � = (1 − 0.9) 100 = 10
0 h
 moles of HCHO formed
Yield =
moles that would have been formed if there
were no side reactions and
limiting reactant is copletely consumed

𝑛𝑛3 mol 𝐻𝐻𝐻𝐻𝐻𝐻𝐻𝐻

Yield = 0.85 = ⇒ 𝑛𝑛3 = 85
100 h

𝑛𝑛5 = 5 𝑛𝑛6 (8)

Atomic species balances:

mol 𝐻𝐻𝐻𝐻𝐻𝐻𝐻𝐻
C 100 = 𝑛𝑛1 + 𝑛𝑛3 + 𝑛𝑛5 + 𝑛𝑛6 ⇒ 𝑛𝑛6 = 0.8333
h
𝐻𝐻2 𝑂𝑂
H 400 = 4 𝑛𝑛1 + 2 𝑛𝑛3 + 2 𝑛𝑛4 ⇒ 𝑛𝑛4 = 95 mol
h
mol
O 200 = 2 𝑛𝑛2 + 𝑛𝑛3 + 𝑛𝑛4 + 2 𝑛𝑛5 + 𝑛𝑛6 ⇒ 𝑛𝑛2 = 5.4135 𝑂𝑂2
h
Problem-3: In the anaerobic fermentation of grain, the yeast digests glucose (𝐶𝐶6 𝐻𝐻12 𝑂𝑂6 ) from plants to
form the products ethanol and propenoic acid (𝐶𝐶2 𝐻𝐻3 𝐶𝐶𝑂𝑂2 𝐻𝐻) by the following overall reactions:
𝐶𝐶6 𝐻𝐻12 𝑂𝑂6 → 2 𝐶𝐶2 𝐻𝐻5 𝑂𝑂𝑂𝑂 + 2 𝐶𝐶𝑂𝑂2
𝐶𝐶6 𝐻𝐻12 𝑂𝑂6 → 2 𝐶𝐶2 𝐻𝐻3 𝐶𝐶𝑂𝑂2 𝐻𝐻 + 2 𝐻𝐻2 𝑂𝑂
In a batch process, a tank is charged with 4000 kg of 12\% solution of glucose in water. After
fermentation, 120 kg of CO2 are produced and 90 kg of unreacted glucose remains in the broth. What are
the mass % of ethanol and propenoic acid in the broth at the end of the fermentation process? Assume
none of the glucose is assimilated into the bacteria (yeast). Solve this problem by using atomic specie
balance approach. While solving using atomic balances you should first evaluate the number of
independent atomic species present.
 Balances for Multi-Phase System
(Single Component: two phase system)

Phase primarily refers to gas, liquid or solid states. Virtually all processes involve transfer of material
from one phase to other phase. For example, soluble constituents of tea leaves are transferred from solid
phase to liquid phase in making a cup of tea in kitchen or transfer of vapor to liquid and liquid to vapor
phase occurs in a distillation column to produce different fuels from crude. Further note that oil in water
(or vice-versa) emulsion also constitutes a two phase system where oil and water (both liquids) forms two
different phases. In such a case if water contains an organic component which is more soluble in oil, then
this component will be transferred from water to oil. In this module, we will discuss material balances in
which one or more component is transferred from one phase to other phase. For most part of this module,
we will restrict ourselves to liquid and vapor phase and assume that the two phases are in thermodynamic
equilibrium with each other. Thermodynamic equilibrium implies mechanical, thermal, and chemical
equilibrium. Mechanical and thermal equilibrium is attained by uniformity in pressure and temperature
respectively in most cases while chemical equilibrium implies constant homogeneous composition
throughout each phase (composition in different phases could be different, but will be constant and
homogeneous throughout each phase). We start our discussion with two-phase single component system.

Intensive variables are those which do not depend on the mass or quantity of system. For example,
density, concentration, specific volume (volume/mass), temperature, pressure, specific enthalpy
(enthalpy/mass) etc.
Extensive variables depend on the size of the system. For example, mass, volume, number of moles etc.

Single component phase equilibrium: Phase diagrams

A pure substance (i.e. substance having homogeneous composition throughout e.g. water, air etc.) exist
in solid, liquid, or gas state for most values of temperature and pressure; but at certain temperature and
pressure values, two (e.g. vapor-liquid, liquid-solid or solid vapor) or all three states may co-exist. For
example, water at 80 oC and 1 atm pressure exist as liquid while at 100 oC and 1 atm can coexist as liquid
water and water vapors. Similarly, at 100 oC and 2 atm, water is a liquid. Phase diagrams for a pure
substance demarcate the regions of different states as pressure, temperature (or any other intensive
variable(s)) are varied. Phase diagrams are plot of an intensive variable with respect to another intensive
variable depicting the phases for a pure substance as the two variables are varied. Let us look at
temperature-specific volume phase diagram to better understand the phase diagrams. Further, let us
assume water as the substance as we are familiar with several processes that occur for water.
Specific volume is plotted on horizontal axis, temperature on vertical axis, and several constant pressure
lines are shown in the left figure of above diagram. Let us consider water at 20oC and 1 atm pressure. We
know from experience that water will exists as liquid at these values of pressure and temperature.
Consider a process in which this sample of liquid water at 20oC and 1atm (point-1 in left figure) is heated
at constant pressure (= 1atm) in closed system (like in a piston-cylinder assembly). As heating process
continues, the specific volume and temperature keeps on increasing until 100 oC (process 1-2). Further
heating causes a generation of water vapor without changing temperature while the specific volume keeps
on increasing with increase in amount of vapors until the whole liquid is vaporized. This process is the
horizontal line for a given pressure with all liquid on the left most point and all vapors on the rightmost
point of horizontal line (process 2-4). Further heating again causes an increase in temperature and specific
volume of the vapor phase (process 4-5). If we perform a similar experiment at a different value of
pressure, we will obtain another set of lines/curves corresponding to a different pressure (refer figure at
right and curves at different pressure values). It is observed that the length of horizontal segment keeps on
decreasing with increasing value of pressure and finally at sufficiently high pressure the horizontal line
reduces to a point. This point is known as critical point. Note that the left most points on the horizontal
lines denote a change from liquid to liquid-vapor mixture and rightmost points denote a change from
liquid-vapor mixture to entire vapors. If we join all end-points of this horizontal line, we obtain a curve
which demarcates the diagram into three regions (refer figure below): liquid region (or compressed liquid
region), saturated liquid-vapor region and superheated vapor region. Thus, we can determine the phase of
a pure substance when any two intensive variables are specified (T and v or T and P or P and v). We can
represent different processes on this diagram. For example, constant pressure process is already shown, a
vertical line represents constant volume process, or a horizontal line represents isothermal process.
Several other phase diagrams are constructed, for example, pressure-specific volume (P-v), pressure-
temperature (P-T), specific enthalpy-specific volume (h-v) etc. A P-T phase diagram including the solid
phase is shown in figure below. It consists of three lines: (1) liquid-vapor equilibrium line demarcating
liquid and vapor regions, (2) solid-liquid equilibrium line, and (3) solid vapor equilibrium line. The three
phases coexist together at a point known as triple point. Point A is all gas (or vapors), C is all liquid, B
and D are liquid-vapor mixtures. The process ABCDE comprises of isothermal decompression of vapor
(A-B) followed by transition from vapor to liquid at constant T and P (point B), isothermal decrease of
pressure (B-C), isobaric heating of liquid (C-D), change of liquid to vapor at constant T and P (point D),
and finally isobaric heating of vapors. Several terms are defined in context of phase diagrams.
Boiling: The change of phase from liquid to vapor represented by point D in P-T diagram or horizontal
lines in T-v diagram.
Condensation: The change of phase from vapor to liquid such as represented by point B in P-T diagram.
Vapor pressure and Boiling point: If T and P correspond to a point on vapor-liquid equilibrium curve, P
is the vapor pressure of the substance at temperature T, and T is referred as boiling point at pressure P. If
P is atmospheric pressure, T is referred as normal boiling point.

Melting or Freezing point: If (T,P) falls on solid-liquid equilibrium curve, then T is melting or freezing
point at P.
Sublimation point: If (T,P) falls on solid-vapor equilibrium line, P is vapor pressure of solid at T and T
is referred as sublimation point at P.
Estimation of vapor pressure: The magnitude of vapor pressure of any substance at a given temperature
indicates the tendency to generate vapors. The substance with higher vapor pressure at a given
temperature will generate more vapors than the one with lower value of vapor pressure at same
temperature. The substance having high vapor pressure (equivalently which produces more vapors) is
referred as more volatile component of the two substances. In the following, we briefly discuss how to
determine (or estimate) the values of vapor pressure at a given temperature, or the temperature given the
vapor pressure.
Using thermodynamic tables such as steam tables for water: This is most accurate method of
determining vapor pressure. We do not describe this method and the reader is referred to any standard text
in Engineering Thermodynamics to understand the same. For example:
Çengel, Yunus A., and Michael A. Boles. 2008. Thermodynamics: an engineering approach., Tata
McGraw-Hill-New Delhi
Himmelbalu, D. M. , and Riggs, J. M.; 2014. Basic priciples and calculations in chemical engineering,
PHI Learning Pvt. Ltd. Delhi.
Using Equations to estimate vapor pressure: Many functional forms of vapor pressure p* as a function
of temperature exist, but we will use a relatively simple equation known as Antoine Equation which
predicts the data extremely well.
𝐵
log10 𝑝∗ = 𝐴 −
𝑇+𝐶
Where T is the temperature in degree centigrade and A, B, and C are constants for a particular substance.
Values of these constants exist in literature for over 5000 compounds. Note that the value of p* obtained
will be in mm of Hg. For water in temperature range of 60 to 150oC: A = 7.96681, B = 1668.21, C =
228.0. You may verify the accuracy of equation by checking the value of vapor pressure at 100 oC at
which the vapor pressure of water is very close to 760 mm Hg.
Problem: Show a constant volume heating process on a T-v diagram if initially the system consists of a
single component liquid-vapor mixture in equilibrium.
Solution:

A constant volume process on a temperature-specific volume (T-v) diagram will be represented by a

vertical straight line. Initial state is given as vapor liquid mixture, thus, the initial state will lie on any of
the possible dotted black horizontal line shown in the above figure (pressure and corresponding saturation
temperature value will determine the position of horizontal line). The dash-dotted vertical line passes
through critical point and the corresponding specific volume is specific volume at critical point or critical
volume. If the initial state lies towards left of this dash-dotted vertical line (given specific volume <
critical volume), the constant volume heating process shown by vertical arrow line depicts that the final
single phase state would be compressed liquid state. On the other hand, if specific volume > critical
specific volume then the vertical arrow on the right shows that the final state would lie in superheated
vapor region.
Problem: Determine the vapor pressure of toluene at 60oC using Antoine equation.
Solution:
For Toluene, Antoine constants A, B, C from tables (like Table B.4 from Richard M. Felder & Ronald W.
Rousseau, Elementary principles of chemical processes, John Wiley and Sons 2000)
𝐴 = 6.95805, 𝐵 = 1346.773, 𝐶 = 219.693
𝐵 1346.773
log10 𝑝∗ = 𝐴 − = 6.95805 −
𝑇+𝐶 60 + 219.693
⇒ 𝑝∗ = 138.95 mm Hg
Problem: The experimental value for normal boiling point of benzene is 80.1oC. Calculate the normal
boiling point of benzene using Antoine equation.
Solution: For Benzene, Antoine constants from Tables (like Table B.4 from Richard M. Felder & Ronald
W. Rousseau, Elementary principles of chemical processes, John Wiley and Sons 2000):
𝐴 = 6.89272, 𝐵 = 1203.531, 𝐶 = 219.888
At normal boiling point, vapor pressure is equal to atmospheric pressure (= 760 mm Hg).
𝐵
log10 𝑝∗ = 𝐴 −
𝑇+𝐶
1203.531
log10 760 = 6.89272 −
𝑇 + 219.888
⇒ 𝑇 = 80.102𝑜 𝐶
 Balances for Multi-Phase System
(Two phase Gas-Liquid System: single condensable component)

Unit's Summary
A representative system that we will consider in this unit is shown in Figure 5.2.1. This figure shows a
closed system containing three or more components present in both liquid and vapor phase. The two
phases are in equilibrium with each other which means that the pressure and temperature is uniform
throughout the system and the composition is uniform in each phase. Note that composition of a species
(e.g A) need not be equal in both liquid and vapor phases. All that is required for chemical equilibrium is
that the composition is homogeneous in both liquid and gas phase. We are interested in applying material
for such type of multi-component system as they undergo a process. Even though we have assumed a
closed system above, the discussion that follows holds for open systems as well.

A, B, C (gas)

A, B, C (liquid)

Figure 5.2.1
The first question that we ask is how to specify such a system i.e. how we should describe this system to
someone else such that he/she will be able to reproduce exactly identical system. Of course we can
specify temperature, pressure, composition of A, B, and C in both phases, and mass of each phase;
however, not all of these variables are independent. Once some variables are specified, other are fixed and
in several cases can be calculated from physical properties of system. The number of intensive variables
that can be specified independently for a system at equilibrium is known as degree of freedom of the
system and the rule that determines degree of freedom is known as Gibbs Phase Rule.
𝑫𝑶𝑭 = 𝟐 + 𝑪 − 𝑷
Where, C = number of components, and P = number of phases in a system at equilibrium.
Gas-Liquid System with one condensable component: Processes like drying, evaporation,
humidification, dehumidification, condensation etc. involve transfer of material from gas to liquid or
liquid to gas phase. More importantly, out of all the components present in these processes, only one is
capable of existing as liquid i.e. it is this component which is present in both liquid and gas phase while
all other exist only in gas phase. For example, water is present as liquid and vapor in evaporation process
while air (or other gases) is present only in gas phase. We are interested in analysis of such type of
systems.
Consider a chamber which initially contains dry air (thus, 𝑝𝐻2 𝑂 = 0) at 60oC and 1 atm pressure. Let
liquid water be introduced into the system while keeping temperature and pressure to be constant. Water
begins to evaporate and the mole fraction of water vapor in gas phase begins to increase thus causing
partial pressure of water in gas phase to rise. The partial pressure will keep on increasing until the partial
pressure of water in gas phase becomes equal to vapor pressure of water at the prevailing system
temperature (assumed T = constant at 60oC). The transfer of water from liquid to gas phase (or vice-versa)
stops at this state and there is no further change in composition of gas (𝑝𝐻2𝑂 becomes constant) or liquid
phase (equilibrium attained). The gas phase is said to be saturated with water as it cannot hold any more
amount of water vapor. Thus, at saturation:
𝑝𝑖 = 𝑦𝑖 𝑃 = 𝑝𝑖∗ (𝑇)
Where, i refers to the only condensable specie present in the system (e.g. water in above example system),
pi is the partial pressure of specie i, P is the total or system pressure, and T is system temperature. The
above equation is referred as Raoult's law for single condensable component.
For such a system with two component and two phases present, the Gibb's DOF is given as:
𝐷𝐹 = 2 + 2 − 2 = 2
Thus, if two variables are specified, the other variables are fixed. In the above example, T and P were
fixed while composition of gas phase was not specified. Note that we know temperature and hence we
know vapor pressure at given temperature. Since, the system pressure P is also fixed, we can use Raoult's
law to determine𝑦𝐻2𝑂 . Thus, the composition of gas phase is fixed and can be determined once we fix two
variables (T and P in this case).
Note:
𝒑𝒊 > 𝒑∗𝒊 (𝑻) ⇒ Not Possible
𝒑𝒊 ≤ 𝒑∗𝒊 (𝑻) ⇒ Possible
If 𝑝𝑖 < 𝑝𝑖∗ (𝑇), the gas is referred as superheated vapor while if 𝑝𝑖 = 𝑝𝑖∗ (𝑇), the gas is saturated with
vapor as it cannot hold anymore vapors.
When partial pressure and vapor pressure are equal, the system is said to be in equilibrium (no change in
composition or other intensive variables).
Dew Point and degrees of superheat:
Consider a gas-liquid system with one condensable component whose gas phase is superheated:
𝑝𝑖 = 𝑦𝑖 𝑃 < 𝑝𝑖∗ (𝑇) (1)
Decreasing temperature at constant pressure will cause a decrease in vapor pressure (as vapor pressure
decreases with decrease in temperature). Eventually, a stage will be reached where 𝑝𝑖 = 𝑦𝑖 𝑃 = 𝑝𝑖∗ (𝑇).
Further cooling without change in composition of gas phase (i.e yi) means that partial pressure will
become greater than vapor pressure which is not possible. Thus, any further cooling will cause
condensation of component capable of condensing. This temperature at which condensation begins when
an isobaric cooling process is followed is known as dew point temperature. Difference between the
temperature of the system and its dew point for a given pressure is known as degrees of superheat.
Note that the condensation can also be caused by isothermal compression. If system is compressed
isothermally, this implies that we are increasing the partial pressure (refer RHS of (1)) and eventually, the
partial pressure will become equal to the vapor pressure. Further, compression will cause condensation so
as to decrease mole fraction of condensable component such that the equality between partial pressure
and vapor pressure is maintained.
Several terms are defined to describe the state of gas containing single condensable component. In all
these definitions, saturation refers to any gas-vapor combination while humidity refers to air-water
system.
𝑝𝑖
relative saturation (humidity) = 𝑠𝑟 (ℎ𝑟 ) = × 100
𝑝𝑖∗
𝑝𝑖 moles of vapor
molal saturation (humidity) = 𝑠𝑚 (ℎ𝑚 ) = × 100 =
𝑃 − 𝑝𝑖 moles of vapor free gas
𝑝𝑖 𝑀𝑖 mass of vapor
Absolute saturation (humidity) = 𝑠𝑎 (ℎ𝑎 ) = × 100 =
(𝑃 − 𝑝𝑖 )𝑀𝑑𝑟𝑦 mass of vapor free gas
Where, Mi and Mdry are molecular weight of condensable component and dry (vapor free) gas,
respectively.
𝑠𝑚 𝑝𝑖 /(𝑃 − 𝑝𝑖 )
% saturation (% humidity) = 𝑠𝑝 (ℎ𝑝 ) = ∗ × 100 = ∗ × 100
𝑠𝑚 𝑝𝑖 /(𝑃 − 𝑝𝑖∗ )𝑖
Problem: Determine the degrees of freedom using Gibb's Phase rule for the following system at
equilibrium: (i) Pure liquid toluene, (ii) a mixture of liquid toluene, vapor toluene, and nitrogen gas, (iii) a
mixture of liquid, solid and water vapor, (iv) a mixture of salt and water designed to achieve a specific
vapor pressure. What variables might be specified in each case?
Solution
𝑫𝑶𝑭 = 𝟐 + 𝑪 − 𝑷
(i) C = 1, P = 1  DOF = 2.
Two intensive variables can be specified independently. Here, temperature and pressure can be specified
independently and once these two are specified other intensive variables like specific volume, specific
enthalpy, specific entropy, internal energy etc are all fixed.
(ii) P = 2, C = 2, DOF = 2.
(Temperature, pressure) or (temperature, mole fraction in gas phase) or (pressure, mole fraction in gas
phase). Any of these three pairs can be specified.
Note if we specify temperature and mole fraction, we can calculate system pressure using Raoult's law:
𝑝𝑇 = 𝑝𝑇∗ (𝑇) ⇒ partial pressure of toluene can be calculated as T is known
𝑦𝑇 𝑃 = 𝑝𝑇 ⇒ P will be known as 𝑦𝑇 is given
(iii) C = 1, P = 3,  DOF = 0;
This implies that no further information can be specified and all intensive variables are fixed. Note that
we are this condition will correspond to triple point where all three phases for a pure component co-exist
in equilibrium with each other.
(iv) C = 2, P = 2;  DOF = 2;
The salt concentration and temperature could be adjusted to achieve a specific value of vapor pressure.
Problem: Liquid benzene is introduced into a vessel containing dry air. The vessel is sealed and
temperature is held constant at 60oC. The contents are allowed to attain equilibrium and the pressure
measured at equilibrium is 1100 mm Hg. (i) Determine the composition of vapor phase. (ii) The lower
and upper flammability limits for benzene in air are 1.2 mole% and 7.8 mole% respectively. Determine
the temperature at which the equilibrium concentration of benzene in gas phase will be equal to upper
flammability limit if the pressure is held constant at 1200 mm Hg (thus, giving us estimates of values of
temperature and pressure which must be avoided to safely store benzene in a container).
Solution:
(i)
𝐷𝑂𝐹 = 2 + 𝐶 − 𝑃 = 2 + 2 − 2 = 2 ⇒ since 𝑇 and 𝑃 are specified
⇒ we can determine all other intensive variables
𝑇 = 60℃, 𝑃 = 1100 mm Hg
Using Raoult's law:
𝑦𝐵 𝑃 = 𝑝𝐵 = 𝑝𝐵∗ (60℃)
Using Antoine equation for benzene:
1211
log10 𝑝𝐵∗ = 6.906 −
𝑇 + 220.8
⇒ 𝑝𝐵∗ = 391.45 mm Hg

Thus, vapor phase composition:

391.45
𝑦𝐵 = = 0.356 mol Benzene/mol
1100

𝑦𝑎𝑖𝑟 = 1 − 𝑦𝐵 = 0.644 mol air/mol

(ii)

𝑦𝐵 = 0.078; ⇒ 𝑝𝐵 = 0.078 × 1200 = 𝑝𝐵∗ (𝑇)

93.6 = 𝑝𝐵∗ (𝑇)

1211
log10 93.6 = 6.906 −
𝑇 + 220.8

𝑇 = 24.6℃
Problem: A stream of humid air at 90oC, 1bar, and 60% relative humidity is fed to a process unit at a rate
of 1000 m3/h.

i. Determine the molar flow rate of dry air and water vapor accompanied with it.
ii. Calculate the dew point temperature and degrees of superheat for this stream of humid air.
iii. If this stream of humid air is cooled to 20oC at constant pressure, calculate the % of water
condensed and final vapor phase composition.
iv. If instead of isobaric cooling, the stream is isothermally compressed to 2 bar in the process,
calculate the percentage condensation.
Solution:
(i)
𝑝𝐻2 𝑂
𝑅𝐻 = 60% ⇒ 60 = ∗ (90℃)
𝑝𝐻2 𝑂

Using Antoine equation for water:

1668.210
log10 𝑝𝐻 ∗2𝑂 = 7.96681 − ⇒ 𝑝𝐻∗ 2 𝑂 (90℃) = 525.86 mm Hg
𝑇 + 228.00
⇒ 𝑝𝐻 2𝑂 = 0.6 × 525.86 = 315.51 mm Hg
𝑝𝐻 2𝑂 315.51
𝑦𝐻2 𝑂 = = = 0.41
𝑃 760
Molar flow rate of humid air (assuming ideal gas law to be valid):
𝑚3
𝑃𝑉 100 𝑘𝑃𝑎 × 1000
𝑛𝐻𝐴 = = ℎ = 33.13 kmol/h
𝑅𝑇 8.314 kPa 𝑚3 /kmol K × (273 + 90)
𝑛𝑑𝑟𝑦 𝑎𝑖𝑟 = (1 − 𝑦𝐻2 𝑂 )𝑛𝐻𝐴 = 19.55 kmol/h
(ii)

𝑝𝐻∗ 2 𝑂 (20℃) 17.53

𝑦𝐻2 𝑂 = = = 0.023
760 760
Applying material balances:
DA balances:
19.55 = 𝑛2 (1 − 𝑦𝐻2 𝑂 ) ⇒ 𝑛2 = 20.02 kmol/h HA
Total balance:
𝑛1 = 33.13 − 20.01 = 13.12 kmol/h 𝐻2 𝑂 (𝑙)
% condensation:
𝑛1
% condensation = × 100 = 96%
13.58
(iv)

Assuming 1 bar = 760 mm Hg (actually slightly higher than 760 mmHg)

𝑝𝐻∗ 2 𝑂 (90℃) 525.86
𝑦𝐻2 𝑂 = = = 0.346
760 × 2 1520

Applying material balances:

DA balances:
19.55 = 𝑛2 (1 − 𝑦𝐻2 𝑂 ) ⇒ 𝑛2 = 29.9 kmol/h HA
Total balance:
𝑛1 = 33.13 − 29.9 = 3.23 kmol/h 𝐻2 𝑂 (𝑙)
% condensation:
𝑛1
% condensation = × 100 = 23.8%
13.58
 Balances for Multi-Phase System
(Multi-component Gas Liquid Systems)

In the last unit, we discussed gas-liquid systems with only a single component being present in both gas
and liquid phase. In this unit, we generalize it to the case where more than one component can be present
in both gas and liquid phases. Such systems are encountered very frequently in chemical industries in
operations like distillation, separation in a stripper or absorption column etc. Since, there are two phases
present, the Gibb's DOF will always be equal to the number of components present (DOF=2+ C  2 = C).
Thus, once the composition of one of the phase and temperature (pressure) are specified, the composition
and pressure (temperature) of other phase get fixed. Recall the case of gas-liquid system with single
condensable component. The distribution of this component was determined by Raoult's law. Similar to
the case of gas-liquid system with single condensable component, considering that we initially have only
gas phase consisting of some no-condensable components (say G) and we introduce a liquid mixture
containing components A, B, C... all of which can be present in both phase. There will be a transfer of
components from liquid phase to gas phase and eventually a situation will be attained where the transfer
from one phase to other phase stops and we say that gas and liquid are in equilibrium with each other (i.e.
T, P and composition in each phase is homogeneous and constant). The distribution of different
components in two phases can be determined by two simple approximate equilibrium relations which, to
be precise, are valid only under certain conditions. However, we will use them in this course because of
their simplicity and illustrative purpose. These simple relations form the basis of more general
relationships. In the following, we follow the convention that xi denotes liquid phase composition and yi
denotes gas phase composition for species i.

A, B, C ...G....
(gas)

A, B, C, ... (liq)

Figure 5.3.1
Raoult's law: For component A present in both the phases, the Raoult's law when the liquid is almost
pure A (i.e. xA → 1) is given as:
𝑝𝐴 = 𝑦𝐴 𝑃 = 𝑥𝐴 𝑝𝐴∗ (𝑇)
Even though it is strictly valid in the limit of xA → 1, it is sometimes valid over entire range of
compositions for mixtures of similar substances, such as alkanes of similar molecular weight. In this
course, we will assume it to be valid for entire range of composition to illustrate the use of such
equilibrium relations in mass balance calculations. Note that when xA = 1, the Raoult's law reduces to the
law given in previous unit for single condensable component.
Henry's law: When xA → 0, i.e. dilute solution of A, and provided that A do not dissociate, ionize or,
react in liquid phase, the Henry's law is:
 𝑝𝐴 = 𝑦𝐴 𝑃 = 𝑥𝐴 𝐻𝐴 (𝑇)
where, HA is Henry's constant for A in a particular solvent. This law is particularly useful when we want
to determine the concentration of a sparingly soluble gas in liquid phase, for example, carbon dioxide in
water etc.
Vapor-Liquid Equilibrium Calculations for Ideal Solutions:
Ideal Solutions: A mixture is considered ideal if all components present in mixture follow Raoult's and
Henry's law.
Recall the constant pressure experiment for a single component system in previous unit (water heated
from 20oC at constant pressure) which was used to develop the T-v phase diagram. The temperature and
specific volume increase until boiling point of liquid, and thereafter vaporization occurs at constant
temperature till all liquid is converted into vapors. We consider similar type of constant pressure
experiment with multi-component liquid mixture (components as A, B, C....). As this liquid mixture is
heated, the temperature of the liquid increases and eventually a temperature value is attained at which first
bubble of vapor is produced. Until this point, the process seems identical to the heating of single
component liquid. However, when liquid contains more than one component, the vapor thus generated
will also contain all the components and the composition of vapor phase for each component will be
different from their liquid phase composition. Further addition of heat will cause more liquid to vaporize
and hence, change of liquid phase composition (each component will have a different tendency to
generate vapors depending on their vapor pressure or volatility). This will produce more vapors with a
different composition accompanied by a change in vaporization temperature. The change in vapor phase
composition and vaporization temperature can be deduced via Gibb's phase rule. If we consider a three
component mixture with known liquid phase composition (we require two compositions/mole fractions to
define composition of three component system) and pressure, the DOF = 3. If liquid and vapor are in
equilibrium and we have already specified three intensive variables (two mole fractions and pressure), all
other intensive variables (i.e. gas phase compositions and temperature) get fixed. Further heating will
change liquid phase composition and since, gas phase composition and temperature of the system depends
on pressure and liquid phase composition, both of these (gas composition and vaporization temperature)
will change. Note the difference in vaporization temperature in contrast to single component system
where both T and P are fixed for phase change operation. We can as well describe a similar cooling
process at constant pressure considering a vapor mixture instead of liquid mixture being present initially.
Further, one can also cause vaporization of liquid mixture (or condensation of vapor mixture) by
decompressing (or compressing) the mixture at constant temperature. Based on the above discussion, we
define few relevant terms in the following paragraph.
Bubble point temperature: is the temperature at which first bubble of vapor is formed when the liquid
mixture is heated slowly at constant pressure.
Dew point temperature: is the temperature at which first drop of liquid is formed when a vapor mixture
is cooled at constant pressure.
Bubble point pressure: is the pressure at which first bubble of vapor is formed when a liquid mixture is
decompressed at constant temperature.
Dew point pressure: is the pressure at which first drop of liquid is formed when a vapor mixture is
compressed at constant temperature.
Now consider an ideal liquid solution with components as A, B, C, .... with known mole fractions xA, xB,
xC,.... If the liquid mixture is heated at constant pressure to its bubble point temperature (Tbp ), any further
addition of heat will cause the formation of first bubble of vapors. Assuming equilibrium conditions exist,
the partial pressure of species can be written by using Raoult's law:
𝑦𝑖 𝑃 = 𝑝𝑖 = 𝑥𝑖 𝑝𝑖∗ (𝑇𝑏𝑝 ); 𝑖 = 𝐴, 𝐵, 𝐶, …. (1)
And the system pressure will be equal to the sum of partial pressures of each component in vapor phase.
𝑃 = 𝑥𝐴 𝑝𝐴∗ (𝑇𝑏𝑝 ) + 𝑥𝐵 𝑝𝐵∗ (𝑇𝑏𝑝 ) + 𝑥𝐶 𝑝𝐶∗ (𝑇𝑏𝑝 ) + … … (2)
Recall that we know P, mole fractions in liquid phase xi and hence, we can calculate Tbp using the above
equation (using a numerical method like Newton-Raphson or trial and error). Once we know bubble point
temperature, we can use equation (1) to calculate mole fractions in vapor phase.
We can use equations (1) and (2) to determine bubble point pressure and composition in vapor phase. A
discussed above, the process here would be decompressing a liquid mixture at constant temperature to
cause vaporization. In this case, T is known while P at which first bubble of vapor would form (i.e.
bubble point pressure Pbp) is unknown variable. Since, we are assuming that all xi and T are known,
pressure calculated using equation (2) will directly give us bubble point pressure. Using this pressure in
(1) will calculate the composition of gas phase.
𝑝𝑖 𝑥𝑖 𝑝𝑖∗ (𝑇) (3)
𝑦𝑖 = =
𝑃𝑏𝑝 𝑃𝑏𝑝
Dew point temperature and pressure can be determined following similar procedure. Suppose a vapor
mixture with known mole fraction is cooled at constant pressure to its dew point temperature (Tdp).
Further cooling causes condensation and the composition of liquid drop produced can be calculated as:
𝑦𝑖 𝑃 (4)
𝑥𝑖 =
𝑝𝑖∗ (𝑇𝑑𝑝 )
Where Tdp will be determined by numerical procedure or trial and error from the following equation:
𝑦𝐴 𝑃 𝑦𝐵 𝑃
𝑥𝐴 + 𝑥𝐵 + 𝑥𝐶 + ⋯ = 1 ⇒ + +⋯=1
𝑝𝐴∗ (𝑇𝑑𝑝 ) 𝑝𝐵∗ (𝑇𝑑𝑝 )
The dew-point pressure is the pressure when the first liquid drop is formed while compressing the system
at constant temperature. Again, T is known in last equation and P = Pdp. Thus dew point pressure from
last equation is:
1
𝑃𝑑𝑝 =
𝑦𝐴 𝑃 𝑦 𝑃
+ 𝐵 + ⋯
𝑝𝐴∗ (𝑇) 𝑝𝐵∗ (𝑇)
Liquid mole-fraction can then be calculated using equation (4).
Problem: Calculate the pressure and liquid phase composition in a gas-liquid water system at equilibrium
in which gas phase constitutes of 98 mole% N2 and 2% water vapors at 80oC.
Solution:
Nitrogen is sparingly soluble in water; hence, Henry's law will be applicable for nitrogen.
Raoult's law will be used for water.
𝑝𝑁 2 = 𝑥𝑁 2 𝐻𝑁 2 (80𝑜 𝐶) = 𝑥 𝐻𝑁 2 (80𝑜 𝐶) (1)
𝑝𝐻2 𝑂 = 𝑥𝐻2 𝑂 𝑝𝐻∗ 2 𝑂 (80𝑜 𝐶) = (1 − 𝑥)𝑝𝐻∗ 2 𝑂 (80𝑜 𝐶) (2)
𝑝𝐻2 𝑂 = 0.02 𝑃 (3)
𝑝𝑁2 = 0.98 𝑃 (4)

Dividing (3) by (4) and substituting partial pressure expression from (1) and (2):
∗ 𝑜
0.02 𝑃 ((1 − 𝑥)𝑝𝐻2 𝑂 (80 𝐶))
=
0.98 𝑃 𝑥 𝐻𝑁 2 (80𝑜 𝐶)
atm
𝐻𝑁2 = 12.6 × 104 (from literature)
mole fraction
Partial pressure of water at 80oC can be calculated using Antoine's equation:
𝑝𝐻∗ 2 𝑂 (80𝑜 𝐶) = 355.1 mm Hg = 0.467 atm

Thus, x can be calculated from last equation.

mol 𝑁2
𝑥 = 1.8158 × 10−4
mol
Thus, partial pressure of N2 from (1):
𝑝𝑁 2 = 1.8158 × 10−4 × 12.6 × 104 = 22.879 atm
𝑝𝑁 2
𝑃= = 23.346 atm
0.98
Note: Henry's law constant for nitrogen and Antoine equation's constant for water will be provided to you
if this question is asked in an examination. Further note that the question can be modified to an air-water
system in equilibrium at 25oC. This means we will have O2 and N2 which are sparingly soluble in water,
and hence, use Henry's law for these two components and Raoult's law for water (consider air in
equilibrium at ambient conditions above a water body, such as lake, for a practical example).
Problem: A gas containing 88% nitrogen, benzene and toluene is in equilibrium with a benzene-toluene
liquid mixture (40 mole% benzene and 60% toluene) at pressure of 10 atm. Calculate the gas phase
composition and temperature of gas and liquid phases.
Solution:
Since the liquid and gas are in equilibrium with each other, the temperature of both phases will be equal.
Raoult's law will be used to calculate temperature and compositions.
𝑃 = 10 𝑎𝑡𝑚 = 7600 mm Hg = 𝑃𝐵 + 𝑃𝑇 + 𝑃𝑁2
Using Raoult's law:
𝑃𝐵 = 𝑦𝐵 𝑃 = 𝑥𝐵 𝑝𝐵∗ (𝑇); 𝑃𝑇 = 𝑦𝑇 𝑃 = 𝑥𝑇 𝑝𝑇∗ (𝑇); 𝑃𝑁2 = 𝑦𝑁2 𝑃

7600 = 𝑥𝐵 𝑝𝐵∗ (𝑇) + 𝑥𝑇 𝑝𝑇∗ (𝑇) + 𝑦𝑁2 𝑃

7600 = 𝑥𝐵 𝑝𝐵∗ (𝑇) + 𝑥𝑇 𝑝𝑇∗ (𝑇) + 0.88 × 7600

912 = 0.4𝑝𝐵∗ (𝑇) + 0.6𝑝𝑇∗ (𝑇) … … … … (1)
1211 (6.906−
1211
)
log10 𝑝𝐵∗ = 6.906 − ⇒ 𝑝𝐵∗ = 10 𝑇+220.8
𝑇 + 220.8
1343.9 (6.9533−
1343.9
)
log10 𝑝𝑇∗ = 6.9533 − ⇒ 𝑝𝑇∗ = 10 𝑇+219.38
𝑇 + 219.38
Substitute vapor pressure of benzene and toluene from Antoine equation in (1), we get a nonlinear
equation in T. This nonlinear equation can be solved by using any numerical technique like Newton-
Raphson or mid-point method. We show briefly the solution by Newton-Raphson method.
Newton-Raphson algorithm:
𝑓(𝑇𝑖 )
𝑇𝑖+1 = 𝑇𝑖 − ; 𝑓𝑜𝑟 𝑛𝑜𝑛𝑙𝑖𝑛𝑒𝑎𝑟 𝑒𝑞𝑢𝑎𝑡𝑖𝑜𝑛 𝑓(𝑇) = 0
𝑓 ′ (𝑇𝑖 )
1211 1343.9
(6.906− ) (6.9533− )
𝑓(𝑇) = 0.4 × 10 𝑇+220.8 + 0.6 × 10 𝑇+219.38 − 912 = 0
Initial guess
𝑇0 = 80℃; This is the normal boiling point of benzene
𝑓(80℃)
𝑇1 = 𝑇0 − = 108.24℃
𝑓 ′ (80℃)
𝑓(108.24℃)
𝑇2 = 𝑇1 − = 101.969℃
𝑓 ′ (108.24℃)
𝑓(101.969℃)
𝑇3 = 𝑇2 − = 101.512℃
𝑓 ′ (101.969℃)
𝑓(101.512℃)
𝑇4 = 𝑇3 − = 101.5094℃
𝑓 ′ (101.512℃)
𝑇5 = 101.5094℃ ⇒ convergence achieved
⇒ equlibrium temperature 𝑇 = 101.509 ℃
Note that the equilibrium temperature calculated above will be the bubble point for the given liquid
mixture (e.g. if 40% benzene and 60% toluene mixture stored in a closed vessel at 10 atm with inert
environment maintained using nitrogen is heated at constant pressure, the temperature at which first
bubble of vapor is formed is the equilibrium temperature calculated above).
𝑝𝐵∗ (101.509℃) = 1406.59 mm Hg; 𝑝𝑇∗ (101.509 ℃) = 582.256 mm Hg
𝑥𝐵 𝑝𝐵∗ (101.509℃)
𝑦𝐵 = = 0.074
𝑃
𝑥𝑇 𝑝𝑇∗ (101.509℃)
𝑦𝑇 = or (1 − 𝑌𝑁2 − 𝑦𝐵 ) = 0.046
𝑃
Problem: A gas contains 7% Benzene, 4.5% toluene, and 88.5% N2 at 10 atm is in equilibrium with
liquid mixture. Calculate the equilibrium temperature (dew point) and liquid composition.
Solution:
For dew point calculations:
𝑥𝐵 + 𝑥𝑇 = 1
𝑦𝐵 𝑃 𝑦𝑇 𝑃
𝑥𝐵 = ∗ (𝑇) ; 𝑥 𝑇 = ∗ (𝑇)
𝑝𝐵 𝑝𝑇
0.07 × 7600 0.045 × 7600
⇒ + = 1 … … … (1)
𝑝𝐵∗ (𝑇) 𝑝𝑇∗ (𝑇)
Using Antoine equation:
1211 (6.906−
1211
)
log10 𝑝𝐵∗ = 6.906 − ⇒ 𝑝𝐵∗ = 10 𝑇+220.8
𝑇 + 220.8
1343.9 (6.9533−
1343.9
)
log10 𝑝𝑇∗ = 6.9533 − ⇒ 𝑝𝑇∗ = 10 𝑇+219.38
𝑇 + 219.38
Put in (1) to get a non-linear equation 𝑓(𝑇) = 0 and solve using Newton-Raphson method.
Different iteration give following values using 80oC as initial guess.
𝑇1 = 94.095℃; 𝑇2 = 99.6503℃; 𝑇3 = 100.29℃; 𝑇4 = 100.298; 𝑇5 = 100.298℃
Thus,
𝑇 = 100.298℃
0.07 × 7600 𝑦𝑇 𝑃
𝑥𝐵 = ∗ (100.298℃) = 0.391; 𝑥 𝑇 = ∗ (100.298℃) = 0.609
𝑝𝐵 𝑝𝑇
Problem: A gas contains 7% Benzene, 4.5% toluene, and 88.5% N2 at 100oC is compressed isothermally
until condensation begins. Calculate the pressure (dew point pressure) at which condensation begins and
the composition of initial condensate.
Solution:
𝑥𝐵 + 𝑥𝑇 = 1
𝑦𝐵 𝑃𝑑𝑝 𝑦𝑇 𝑃𝑑𝑝
𝑥𝐵 = ∗ (100℃) ; 𝑥𝑇 = ∗ (100℃)
𝑝𝐵 𝑝𝑇

0.07𝑃𝑑𝑝 0.045𝑃𝑑𝑝
⇒ + =1
1350.49 556.321

𝑃𝑑𝑝 = 7534.57 mm Hg = 9.91 𝑎𝑡𝑚

𝑦𝐵 𝑃𝑑𝑝 0.07 × 7534.57 𝑦𝑇 𝑃𝑑𝑝 0.045 × 7534.57

𝑥𝐵 = ∗ (100℃) = = 0.3905; 𝑥𝑇 = ∗ = = 0.6095
𝑝𝐵 1350.49 𝑝𝑇 (100℃) 556.321
Problem: Consider a binary liquid mixture of benzene and toluene in equilibrium with its vapor at a
given P (= 1atm). The composition of more volatile component (i.e. benzene in this case) is denoted by x
in liquid phase and by y in vapor phase. Note that the DOF = 2+2-2=2. This implies that if two intensive
properties are specified, all other intensive properties of the system can be determined. Pressure is already
fixed at 1 atm. If we now fix the mole fraction of benzene in the liquid phase, the composition of vapor
phase and the equilibrium temperature can be determined for the corresponding P and x. Consider x to
vary from 0 to 1, calculate the corresponding composition in vapor phase and equilibrium temperature.
Construct temperature vs. composition curve for this system.

Solution

Given P = 1 atm and liquid phase benzene compositions:

Let us make calculation for the following values of x:

𝑥𝑥 = 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0

We are required to calculate y and T for each x.

x = 0 implies pure toluene present as liquid and is in equilibrium with its vapor

This implies y=0 and for toluene: mole fraction in both phases is 1. The equilibrium temperature is the
normal boiling point of toluene = 110.62 oC

x = 1 implies pure benzene in both liquid and vapor phases. Thus, y = 1, and equilibrium temperature is
normal boiling point (since P = 1 atm) of benzene = 80.1 oC.

For all other values of x, we are required to calculate bubble point temperature and composition in vapor
phase i.e y and (1-y).

For bubble point calculations for a multi-component system:

𝑃𝑃 = 𝑥𝑥𝐴𝐴 𝑝𝑝𝐴𝐴∗ �𝑇𝑇𝑏𝑏𝑏𝑏 � + 𝑥𝑥𝐵𝐵 𝑝𝑝𝐵𝐵∗ �𝑇𝑇𝑏𝑏𝑏𝑏 � + 𝑥𝑥𝐶𝐶 𝑝𝑝𝐶𝐶∗ �𝑇𝑇𝑏𝑏𝑏𝑏 � + … …

For binary mixture of Benzene (denoted as B) and toluene (denoted as T):

𝑃𝑃 = 𝑥𝑥𝐵𝐵 𝑝𝑝𝐵𝐵∗ �𝑇𝑇𝑏𝑏𝑏𝑏 � + 𝑥𝑥𝑇𝑇 𝑝𝑝𝑇𝑇∗ �𝑇𝑇𝑏𝑏𝑏𝑏 � = 𝑥𝑥𝑝𝑝𝐵𝐵∗ �𝑇𝑇𝑏𝑏𝑏𝑏 � + (1 − 𝑥𝑥)𝑝𝑝𝑇𝑇∗ �𝑇𝑇𝑏𝑏𝑏𝑏 �

For x = 0.1 and P = 1 atm = 760 mm Hg;

760 = 0.1𝑝𝑝𝐵𝐵∗ �𝑇𝑇𝑏𝑏𝑏𝑏 � + (1 − 0.1)𝑝𝑝𝑇𝑇∗ �𝑇𝑇𝑏𝑏𝑏𝑏 �

Using Antoine equation vapor pressure at any given temperature T:

1211 �6.906−
1211
�
log10 𝑝𝑝𝐵𝐵∗ = 6.906 − ⇒ 𝑝𝑝𝐵𝐵∗ = 10 𝑇𝑇+220.8
𝑇𝑇 + 220.8
1343.9 �6.9533−
1343 .9
�
log10 𝑝𝑝𝑇𝑇∗ = 6.9533 − ⇒ 𝑝𝑝𝑇𝑇∗ = 10 𝑇𝑇+219.38
𝑇𝑇 + 219.38
 1211 1343.9
�6.906− � �6.9533− �
𝑇𝑇𝑏𝑏𝑏𝑏 +220.8 𝑇𝑇𝑏𝑏𝑏𝑏 +219.38
760 = 0.1 × 10 + 0.9 × 10

Solve the above equation by using Newton-Raphson technique:

𝑓𝑓(𝑇𝑇𝑖𝑖 )
𝑇𝑇𝑖𝑖+1 = 𝑇𝑇𝑖𝑖 − ; 𝑓𝑓𝑓𝑓𝑓𝑓 𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛 𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒 𝑓𝑓(𝑇𝑇) = 0
𝑓𝑓 ′ (𝑇𝑇𝑖𝑖 )
1211 1343.9
�6.906− � �6.9533− �
𝑇𝑇𝑏𝑏𝑏𝑏 +220.8 𝑇𝑇𝑏𝑏𝑏𝑏 +219.38
𝑓𝑓(𝑇𝑇) = 0.1 × 10 + 0.9 × 10 − 760 = 0
Initial guess
𝑇𝑇0 = 110℃; This is the normal boiling point of toluene
𝑓𝑓(𝑇𝑇0 )
𝑇𝑇1 = 𝑇𝑇0 − = 106.28℃
𝑓𝑓 ′ (𝑇𝑇0 )
𝑓𝑓(𝑇𝑇1 )
𝑇𝑇2 = 𝑇𝑇1 − = 106.118℃
𝑓𝑓 ′ (𝑇𝑇1 )
𝑓𝑓(𝑇𝑇2 )
𝑇𝑇3 = 𝑇𝑇2 − = 106.118℃
𝑓𝑓 ′ (𝑇𝑇2 )
⇒ equlibrium temperature 𝑇𝑇 = 106.118℃

𝑥𝑥𝑝𝑝𝐵𝐵∗ (106.118)
𝑦𝑦 = = 0.209 mol Benz/mol
𝑃𝑃
Similar calculations are performed for other values of x and the final results are tabulated below:

x 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9

T 106.12 102.08 98.43 95.11 92.07 89.29 86.72 84.34 82.12
y 0.209 0.376 0.511 0.622 0.714 0.791 0.856 0.911 0.959

The plot of T vs x and y is shown in figure below. Such a plot is known as T-x-y curve for a binary
mixture where bubble point and dew point temperatures are plotted as a function of mole fraction of more
volatile component.
Problem: A methanol-water feed stream enters a vaporizer at a rate of 150 mol/min, where it is partially
vaporized, and the vapor and liquid streams emerging from the device are in equilibrium with each other.
The vaporizer operates at 1 atm and 80oC, and the mole fraction of methanol in the feed is 0.4 mol
methanol/mol. Calculate the flow rate and compositions of vapor and liquid stream leaving the vaporizer.
A T-x-y diagram for methanol-water system at 1 atm is shown below. Also outline the calculation
procedure if the T-x-y plot is not available.

Solution

Labeled flowchart:

We are given T-x-y plot for methanol-water system. The vapor and liquid stream leaving the vaporizer are
in equilibrium with each other at 80oC and 1 atm. The mole fractions of methanol in liquid and vapor
phase from the T-x-y plot are:

𝑥𝑥 = 0.24 (corresponding to point A); 𝑦𝑦 = 0.61 (point C)

Total and methanol balance:

150 = 𝑛𝑛𝑣𝑣 + 𝑛𝑛𝑙𝑙 ; 150 × 0.4 = 0.61𝑛𝑛𝑣𝑣 + 0.24𝑛𝑛𝑙𝑙

⇒ 𝑛𝑛𝑣𝑣 = 64.8 mol/min; 𝑛𝑛𝑙𝑙 = 85.2 mol/min

Note: if T-x-y plot was not available, we would have used the following equations:
 𝑃𝑃 = 1 𝑎𝑎𝑎𝑎𝑎𝑎 = 760 𝑚𝑚𝑚𝑚 𝐻𝐻𝐻𝐻 = 𝑃𝑃𝑀𝑀 + 𝑃𝑃𝑤𝑤𝑤𝑤𝑤𝑤𝑤𝑤𝑤𝑤
∗ (80℃) ∗
⇒ 760 = 𝑥𝑥𝑝𝑝𝑀𝑀 + (1 − 𝑥𝑥)𝑝𝑝𝑤𝑤𝑤𝑤𝑤𝑤𝑤𝑤𝑤𝑤 (80℃); (Raoult's law)
∗ (80℃) ∗ (80℃) is to be calculated using Antoine
Vapor pressure for methanol 𝑝𝑝𝑀𝑀 and water 𝑝𝑝𝑤𝑤𝑤𝑤𝑤𝑤𝑤𝑤𝑤𝑤
equation. Substituting in above equation will yield the value of x. The value of y is then calculated as:
∗ (80℃)
𝑥𝑥𝑝𝑝𝑀𝑀
𝑦𝑦 =
𝑃𝑃(= 760 𝑚𝑚𝑚𝑚 𝐻𝐻𝐻𝐻)

Finally write the total and methanol balance to solve for vapor and liquid flow rates.
 Fundamentals of Energy Balances
Energy Balance equation for closed and open system)

Recall the general balance equation:

Accumulation within the system= Input via system boundaries - output via system boundaries +
generation within the system - consumption within the system.
Since energy cannot be created or destroyed, the generation and consumption term will drop out from the
above equation:
Accumulation within the system = Input via system boundaries - output via system boundaries
We first write down the integral energy balance equation for a closed system between two instants of
time. Consider an arbitrary system (refer figure below) in which mass exchange is not allowed, but energy
can cross the boundaries of the system. An example process that can be kept in mind is heating of water
in a closed pan where water vapor cannot escape outside of the pan. The closed system then comprises of
the contents (liquid water and water vapor) present in the pan at any given instant of time. We want to
write down the energy balance between two instants of time (say, between 𝑡𝑖𝑛𝑖𝑡𝑖𝑎𝑙 and 𝑡𝑓𝑖𝑛𝑎𝑙 ). Thus,
accumulation within the system = final system energy − initial system energy
The total energy of the system at any given instant of time is defined as sum of internal, kinetic, and
potential energy (𝐸 = 𝑈 + 𝐸𝑘 + 𝐸𝑝 ). This implies:
accumulation within the system = (𝑈 + 𝐸𝑘 + 𝐸𝑝 ) − (𝑈 + 𝐸𝑘 + 𝐸𝑝 ) = ∆𝐸
𝑓 𝑖
For a closed system, energy can cross boundaries by two mechanisms namely heat and work transfer. If Q
represents the net amount of heat transferred to the system and W represents the net amount of work
done by the system, then 𝑄 − 𝑊 represents the net increase in energy of the system in a given duration
of time and this must be equal to accumulation term.
∆𝐸 = ∆(𝑈 + 𝐸𝑘 + 𝐸𝑝 ) = 𝑄 − 𝑊 (1)
The changes in KE and PE are usually negligible in comparison to changes in internal energy, hence, the
closed system energy balance is frequently written as:
∆𝑈 = 𝑄 − 𝑊

𝑊
Control Volume
CV

𝑄
Energy Balance for open system:
An open system by definition allows exchange of both mass and energy across system boundaries. We
usually encounter continuously flowing open systems in industry rather than non-flowing semi-batch type
of open systems. For example, processes/systems like a reaction system where reactant and product
streams continuously enter and leave the reactor are more common than a reaction system where the
reactant and products are intermittently taken out or fed into the system. Thus, we write down energy
balance in a form which is suitable for such continuously flowing open systems. Further, note that we will
write down an energy balance for whole system rather than a point (at a particular spatial location)
balance as written in courses like transport phenomena or heat transfer. Thus, our analysis will give
overall heat and work requirements to carry out the processes. For example, if an exothermic reaction is
carried out in a tubular reactor at a constant temperature of 50℃, our analysis will provide answers like
the heat removal rate required to maintain the constant temperature. The analysis presented in the
following section will not give details like what is temperature at a particular spatial location in a tubular
reactor? Further, for continuously flowing open systems, we use rate of (energy/mass) transfers in
contrast to amount (of mass/heat/work/energy) transferred in a given duration of time. Keeping the above
points in mind, the energy balance for continuous-flow open system can be written in a manner similar to
closed system energy balance:
𝑑𝐸𝑐𝑣
𝑑𝑡
= rate of energy in the system − rate of energy out of the system (2)

𝑚̇𝑖𝑛
𝑊̇
Control Volume
CV

𝑚̇𝑜𝑢𝑡
𝑄̇

The above figure shows an arbitrary shaped open system. Note that inflow and outflow mass flows are
included as compared to the closed system where there were no streams of 𝑚̇𝑖𝑛 and 𝑚̇𝑜𝑢𝑡 . This could
represent any equipment (e.g. a CSTR, tubular reactor, heat exchanger, distillation column etc). There
could be multiple inlet and outlet streams for material entering and leaving the system. 𝑄̇ and 𝑊̇ are the
net rate of heat transfer to the system and net rate of work done by the system. In order to clarify the
differences in writing down the energy balance for flow system as compared to a closed system, let us
consider a simple system with one inlet and one exit stream as shown below:
 Out

𝑄̇ 𝑊̇

in

The system boundaries are shown by dotted lines and the material within the dotted lines comprises the
system under consideration. Note that because of an inflow and exit stream, the material within the dotted
lines keep on exchanging with surroundings. We write energy balance at any given instant of time. The
total energy content of the material present within the system at any given instant of time is given as
𝐸𝑐𝑣 = 𝑈 + 𝐸𝑘 + 𝐸𝑝 = 𝑚𝑐𝑣 (𝑈 ̂+𝐸 ̂𝑘 + 𝐸 ̂𝑝 ), where ̂ represent specific quantities (per unit mass). Now
consider the small chunk of mass that is just about to enter into the system (shown by blue colored box).
The specific total energy content of this small quantity of mass will be (𝑈 ̂+𝐸 ̂𝑘 + 𝐸
̂𝑝 ), however, it
delivers some boundary movement work to the system as this small mass is pushed inside the system by
the mass behind it. In a similar manner, the system does some work in pushing the mass out of the system
at exit. This rate of work transfer at in and exit points is referred as flow work and it must be accounted in
the (rate of energy in) and (rate of energy out) terms in energy balance equation. The rate of flow work
can be written as: 𝑊𝑓𝑙𝑜𝑤 ̇ = 𝐹𝑜𝑟𝑐𝑒 × 𝑣𝑒𝑙𝑜𝑐𝑖𝑡𝑦 = 𝐹 𝑣 = 𝐹 (𝐴 𝑣) = 𝑃𝑉̇ , where 𝑉̇ represents the
𝐴
volumetric flow rate and 𝑃 is the pressure. Thus, 𝑊̇𝑓𝑙𝑜𝑤 = 𝑃𝑉̇ = 𝑃𝑉̂ 𝑚̇, where 𝑉̂ is the specific volume
𝑊̇
̂ = = 𝑃 𝑉̂ .
(𝑚3 /𝑘𝑔 ) and 𝑚̇ is the mass flow rate (𝑘𝑔/𝑠) . The specific work transfer is then 𝑊 𝑚̇

̂ + 𝐸̂𝑘 + 𝐸̂𝑝 + 𝑃𝑉̂ ) =

The rate of total energy entering into the system due to inflow of mass = 𝑚̇𝑖𝑛 (𝑈 𝑖𝑛
̂ + 𝐸̂𝑘 + 𝐸̂𝑝 ) . Similarly, the rate of total energy leaving the system due to outflow of mass =
𝑚̇𝑖𝑛 (𝐻 𝑖𝑛
̂ + 𝐸̂𝑘 + 𝐸̂𝑝 + 𝑃𝑉̂ )
𝑚̇𝑜𝑢𝑡 (𝑈 ̂ + 𝐸̂𝑘 + 𝐸̂𝑝 ) . Thus,
= 𝑚̇𝑜𝑢𝑡 (𝐻
𝑜𝑢𝑡 𝑜𝑢𝑡

net rate in = 𝑄̇ + 𝑚̇𝑖𝑛 (𝐻

̂ + 𝐸̂𝑘 + 𝐸̂𝑝 )
𝑖𝑛

net rate out = 𝑊̇ + 𝑚̇𝑜𝑢𝑡 (𝐻

̂ + 𝐸̂𝑘 + 𝐸̂𝑝 )
𝑜𝑢𝑡

Substituting all the terms in energy balance equation (2):

𝑑𝐸𝑐𝑣
= 𝑄̇ − 𝑊̇ + 𝑚̇𝑖𝑛 (𝐻
̂ + 𝐸̂𝑘 + 𝐸̂𝑝 ) − 𝑚̇𝑜𝑢𝑡 (𝐻
̂ + 𝐸̂𝑘 + 𝐸̂𝑝 )
𝑑𝑡 𝑖𝑛 𝑜𝑢𝑡

If there are multiple inlets and exit streams:

 𝑑𝐸𝑐𝑣 ̇
= 𝑄̇ − 𝑊̇ + ∑ 𝑚𝑖𝑛 (𝐻
̂ + 𝐸̂𝑘 + 𝐸̂𝑝 ) − ∑ 𝑚̇𝑜𝑢𝑡 (𝐻
̂ + 𝐸̂𝑘 + 𝐸̂𝑝 )
𝑑𝑡 𝑖𝑛 𝑜𝑢𝑡
𝑖𝑛 𝑜𝑢𝑡

If the system operates at steady state:

̇
𝑄̇ − 𝑊̇ = ∑ 𝑚𝑜𝑢𝑡 (𝐻
̂ + 𝐸̂𝑘 + 𝐸̂𝑝 ) − ∑ 𝑚̇𝑖𝑛 (𝐻
𝑜𝑢𝑡
̂ + 𝐸̂𝑘 + 𝐸̂𝑝 )
𝑖𝑛
𝑜𝑢𝑡 𝑖𝑛

𝑄̇ − 𝑊̇ = ∆𝐻̇ + ∆𝐸̇𝑘 + ∆𝐸̇𝑝 (3)

Where,

∆𝐻̇ = ∑ 𝑚̇𝑜𝑢𝑡 𝐻
̂𝑜𝑢𝑡 − ∑ 𝑚̇𝑖𝑛 𝐻
̂𝑖𝑛 , ∆𝐸𝑘̇ = ∑ 𝑚̇𝑜𝑢𝑡 𝐸
̂𝑘
𝑜𝑢𝑡
− ∑ 𝑚̇𝑖𝑛 𝐸̂
𝑘 𝑖𝑛 , ∆𝐻
̇
𝑜𝑢𝑡 𝑖𝑛 𝑜𝑢𝑡 𝑖𝑛

= ∑ 𝑚̇𝑜𝑢𝑡 𝐸̂𝑝 − ∑ 𝑚̇𝑖𝑛 𝐸̂𝑝

𝑜𝑢𝑡 𝑖𝑛
𝑜𝑢𝑡 𝑖𝑛

Usually, the changes in enthalpy are significantly larger than changes in kinetic and potential energies and
hence are neglected. For such cases: 𝑄̇ − 𝑊̇ = ∆𝐻̇.

Once we identify the type of system (i.e. closed or open), use and simplify the appropriate form of energy
balance (i.e. Eq (1) for closed system and Eq. (2) for open system) according to the problem statement. A
typical energy balance problem for a closed system will be something like: a material at given initial
conditions is heated from 25℃ to 100℃ (with some final conditions given), calculate the amount of heat
required. Eq (1) is to be used for closed system and this equation shows that we are required to determine
the change in internal energy ∆𝑈 and 𝑊 to determine 𝑄.

For open system, a liquid is being heated in double pipe heat-exchanger from 20℃ to 80℃ by using
saturated steam flowing in outer pipe at a rate of 10 kg/min. The liquid flowing in inner pipe is flowing at
a rate of 4 kg/min. Calculate the amount of heat transferred from steam to water. Eq (3) must be used for
this problem. We are required to determine 𝑊, ∆𝐻̇ , ∆𝐸̇𝑘 , ∆𝐸̇𝑝 to calculate 𝑄̇ . The numerical value of work
transfer is usually given in many cases when shaft work or electrical work or any other mechanical work
is involved. The boundary movement work is determined using 𝑊 = ∫ 𝐹⃗ . 𝑑𝑥⃗. ∆𝐸𝑘 , and ∆𝐸𝑝 can be easily
calculated by knowing velocities and relative positions (vertical heights). Thus, the energy balance
problem essentially boils down to calculating ∆𝑈 for closed systems and ∆𝐻̇ for open systems. We will
discuss the calculations of changes of internal energy and enthalpy in the next unit.
Problem - 1: 1 kg ideal gas in contained in a piston cylinder assembly and the piston is fixed by using a
clamp. The initial temperature of gas is 25℃ with (𝑈 ̂ = 250 kJ , 𝐻
̂ = 340 kJ ). The gas is heated to a
kg kg
kJ kJ
̂ = 510
temperature of 80℃, and specific internal energy and enthalpy in this state are (𝑈 ̂
,𝐻 = 620 ).
kg kg
Calculate the amount of heat supplied to the gas. What changes will occur in calculation of amount of
heat if the gas is allowed to expand freely to 80℃ instead of keeping the piston fixed by a clamp?

Solution:

Given system is a closed system, therefore:

∆𝐸 = ∆(𝑈 + 𝐸𝑘 + 𝐸𝑝 ) = 𝑄 − 𝑊

Assuming negligible changes in KE and PE: ∆𝑈 = 𝑄 − 𝑊

When piston is held in fixed position ⇒ no boundary movement work ⇒ 𝑊 = 0.

̂1 = 250 kJ ; final state 𝑈

Initial state: 𝑈 ̂2 = 510 kJ ⇒ ∆𝑈 = 𝑚(𝑈 ̂1 ) = 1 kg×260 kJ
̂2 − 𝑈
kg kg kg

𝑄 = ∆𝑈 + 𝑊 = 260 + 0 = +260 kJ

Positive sign denotes that heat is transferred to the system.

When the gas is allowed to expand freely, it expands against constant atmospheric pressure. This process
involves a boundary movement work (⇒ 𝑊 ≠ 0). Further, note that since the gas is ideal and initial and
final temperatures do not change, thus, there will be no change in initial and final internal energies (since,
internal energy is only a function of temperature for ideal gases).

𝑄 = ∆𝑈 + 𝑊 = 260 + 𝑃∆𝑉
𝑚 1
Using ideal gas law: 𝑃∆𝑉 = 𝑃 (𝑉2 − 𝑉1 ) = 𝑛𝑅(𝑇2 − 𝑇1 ) = 𝑅(𝑇2 − 𝑇1 ) = 8.314 × (353 − 298)
𝑀𝑊 𝑀𝑊

If the gas is nitrogen (MW = 28kg/kmol)

1 kg kJ
𝑃∆𝑉 = × 8.314 × (353 − 298)K = 16.33 kJ
kg kmol-K
28
kmol

𝑄 = 260 + 16.33 = 276.33 kJ

Note that the values of internal energies in initial and final states were given in this problem. This is
usually not the case and we have to determine internal energies using tables or by using formulas. We will
cover this aspect in next unit of this module.
Problem - 2: 400 kg/h of steam enters a turbine at 45atm and 470℃ at a velocity of 60 m/s. The steam
expands in the turbine and delivers a work at a rate of 65 kW and leaves the turbine at a velocity of 350
m/s at a point 10 m below the inlet point at atmospheric pressure. The heat loss from the turbine is
estimated to be 12 kW. Calculate the specific enthalpy change associated with the process.

Solution

400 kg/h
400 kg/h, 1atm, 350 m/s
45 atm, 470℃,
10 m below entry point.
60m/s

𝑄̇ = −12 𝑘𝑊, 𝑊̇𝑠 = 65kW

System: Steam present in turbine at any given instant of time.

Open system ⇒ 𝑄̇ − 𝑊̇ = ∆𝐻̇ + ∆𝐸̇𝑘 + ∆𝐸̇𝑝

𝑄̇ = −12 kW (negative becuase heat is lost)

𝑊̇𝑠 = 65 kW (positive becuase work is done by the expanding steam)

1 2
∆𝐸̇𝑘 = 2
𝑚̇(𝑢𝑜𝑢𝑡 − 𝑢𝑖𝑛 )
2
400
𝑚̇ = kg/s = 0.1111 kg/s
3600

𝑢𝑜𝑢𝑡 = 350 m/s, 𝑢𝑖𝑛 = 60 m/s

∆𝐸̇𝑘 = 6605.6 J/s = 6.5056 kW

∆𝐸̇𝑝 = 𝑚̇𝑔(𝑧2 − 𝑧1 ) = 0.1111 × 9.8 × (−10 − 0) = 10.9 J/s = −1.09 × 10−2 kW

⇒ ∆𝐻̇ = 𝑄̇ − 𝑊̇ − ∆𝐸̇𝑘 − ∆𝐸̇𝑝 = −12 − 65 − 6.5 + 1.09 × 10−2 = −83.5 kW

83.5
̂= −
specific enthalpy change = ∆𝐻 = −751.5 kJ/kg
0.1111

Note: It is important to note the relative magnitudes of change in enthalpy, change in KE, and change in
PE. The change in PE is negligible (−0.001 kW) as compared to change in enthalpy (−83.5 kW) . The
change in KE is small but is certainly not negligible. However, the velocities were significantly high in
this example. Such high velocities are encountered in equipments like turbine, nozzles etc. Usually the
velocities are much lower than this value in reactors, heat-exchangers, other process equipments and thus,
changes in KE are also usually neglected. If the exit velocity is 120 m/s (still a very high velocity) ⇒
1
∆𝐸̇𝑘 = × 0.1111(1202 − 602 ) = 599 J/s = 0.599 kW which is small as compared to changes in
2
enthalpy.
 Fundamentals of Energy Balances
Calculation of enthalpy and internal energy changes using thermodynamics tables)

Recall the energy balance equations discussed in previous unit.

For closed system:
∆𝑈 = 𝑄 − 𝑊
For steady state continuous flow open system:
𝑄̇ − 𝑊̇ = ∆𝐻̇ + ∆𝐸̇𝑘 + ∆𝐸̇𝑝
The use of both of these equations requires calculations of changes in internal energy and enthalpies i.e.:
∆𝑈 = 𝑚(𝑈 ̂2 − 𝑈 ̂1 ), and ∆𝐻̇ = 𝑚̇(𝐻
̂2 − 𝐻̂1 )
The values of specific internal energy and specific enthalpy in initial (inlet for open systems) and final
(exit states for open system) states were provided in the problem statement for the numerical given in
previous unit. However, often these values are not directly given and these values are to be determined
based on the process by either using thermodynamic tables or by using analytical or empirical relations.
The objective of this unit is to discuss the determination of specific internal energy and enthalpy for a
pure substance in a given thermodynamic state by using thermodynamic tables. In order to better
understand use of thermodynamic tables, let us briefly recap some definitions/concepts which were
introduced earlier in module of multi-phase systems. It is also a suggested to go through the Unit-1 of
Module on Balances on multi-phase systems.
Pure substance: A substance that has a fixed chemical composition throughout. For example, liquid
water in closed container, air in a container, liquid-vapor mixture of water (two phases but same chemical
composition throughout: water mass fraction is unity everywhere) are all examples of pure substance. A
mixture of benzene and toluene in equilibrium with its vapor will not be an example of pure substance
because the composition of benzene and toluene in liquid and vapor phases will be different.
State: implies conditions of a system (specified by the values of temperature, pressure, composition,
phase etc.). Consider an example of water in a piston-cylinder assembly as system in a given state-1. This
implies that all the intensive properties of the system are fixed at a particular value say P 1, T1, (specific
volume)1, (specific enthalpy)1, (specific entropy)1, (specific internal energy)1 etc. The next question is
how many properties we can fix to completely determine the state of the system (or equivalently all other
intensive properties). The answer is given by Duhem's rule and the number of independent intensive
properties that can be fixed independently is TWO to completely lock the state of the system. In
other words, if we fix any two independent intensive properties, all other properties can be determined
by this information and their values are fixed. The details of derivation of Duhem's rule can be found be
in any book on thermodynamics, for example, refer:
J.M. Smith, H.C. Van Ness and M.M. Abbott, Introduction to Chemical Engineering Thermodynamics,
6th ed., McGraw-Hill, 2001.

Recall the phase diagram of a pure substance (excluding the solid region). The whole region was divided
into three regions: compressed liquid (or simply liquid), a liquid-vapor region, and super-heated vapor (or
simply vapor) region. The thermodynamic tables are reported separately for these three regions. We will
first start with liquid-vapor region (region under dome shaped curve in figure below). It is important to
remember that pressure and temperature are not two independent intensive properties in this region.
Recall the piston-cylinder assembly experiment of heating water at constant pressure. Water start
converting to vapor at 100oC at 1atm and we cannot change temperature the resulting liquid-vapor
mixture of water at 1 atm until all liquid water is changed to water vapor. Once all liquid is converted to
vapors, the pressure and temperature can be varied independently.

Figure: A typical phase diagram of a pure substance

A sample of thermodynamic table for water in liquid-vapor region is shown in the following table:
 Table-1
The above table is referred as Temperature-based table. For each temperature value, corresponding
saturation values of pressure, specific internal energy and specific enthalpies are given.
̂𝑙 (𝐻
𝑈 ̂𝑙 ) = specific internal energy (enthalpy) of saturated liquid
𝑈̂𝑔 (𝐻̂𝑣 ) = specific internal energy (enthalpy) of saturated vapor
̂𝑙𝑣 = 𝑈
𝑈 ̂𝑣 − 𝑈
̂𝑙 ; similarly for specific enthalpy and volume
Since we are dealing with liquid-vapor region, we define an intensive variable called as quality (x) which
quantifies the relative amount of liquid and vapor present in the system. Note that quality is defined only
for liquid-vapor mixture region and is not a valid variable in liquid or vapor region.
mass of vapor 𝑚𝑣 𝑚𝑣
𝑥= = = ⇒0≤𝑥≤1
total mass 𝑚𝑙 + 𝑚𝑣 𝑚
𝐻 = 𝐻𝑙 + 𝐻𝑣 = 𝑚𝑙 𝐻 ̂𝑙 + 𝑚𝑣 𝐻̂𝑣
𝐻 𝑚𝐻 ̂ + 𝑚𝑣 𝐻 ̂𝑣 (𝑚 − 𝑚𝑣 )𝐻 ̂𝑙 + 𝑚𝑣 𝐻
̂𝑣
̂= = 𝑙 𝑙
𝐻 =
𝑚 𝑚 𝑚
𝐻̂ = (1 − 𝑥)𝐻 ̂𝑙 + 𝑥 𝐻̂𝑣 = 𝐻̂𝑙 + 𝑥𝐻 ̂𝑙𝑣 , where 𝐻
̂𝑙𝑣 = (𝐻
̂𝑣 − 𝐻̂𝑙 )
̂=𝑈
similarly:𝑈 ̂𝑙 + 𝑥𝑈̂𝑙𝑣
The above nomenclature is shown schematically in the following figure (in terms of specific volume):

Similar to temperature based tables, pressure based thermodynamic tables are also given (see table
below).
 Table-2

The property of a substance when both the liquid and vapor phase co-exist in equilibrium with each other
is determined based on the problem statement. The quality is determined based on the problem statement
and then corresponding saturated values are used from tables to find specific internal energy or specific
enthalpy of the liquid-vapor mixture. The procedure will become clear when we look at the problems
given in this unit. Note that if either of the following condition is satisfied
𝑉̂𝑙 < 𝑉̂ < 𝑉̂𝑣 or 𝑈
̂𝑙 < 𝑈 ̂< 𝑈 ̂𝑣 or 𝐻̂𝑙 < 𝐻
̂<𝐻 ̂𝑣 or similar condition for entropy etc.
the substance exist as liquid-vapor mixture in equilibrium.
The other two zones are liquid and vapor regions. Let us first present sample table for vapor region.
Recall for vapor region, both T and P are independent intensive properties and if we fix two independent
intensive properties to lock the state of the system. Note that the two tables are given for two different
values of pressure. If P = 0.01 MPa, then choosing T at any value (say T=100 oC) fixes the value of other
properties reported in the corresponding row (specific volume = 17.196 cu.m/kg, specific enthalpy =
2687.5 kJ/kg, specific internal energy = 2515.5 kJ/kg, specific entropy = 8.4489 kJ/kg-K for P = 0.01
MPa and T = 100oC).
 Table - 3
The conditions that characterize superheated vapor region are summarized in the figure below:

The tables for compressed liquid or liquid region are presented in a similar manner as they are presented
for vapor region. Both pressure and temperature are two independent intensive properties in this region.
However, the properties depend more strongly on temperature and weakly on pressure variations. Thus,
the effect of pressure is usually neglected and at a given temperature and pressure, the properties are
approximated as:
𝑉̂ = 𝑉̂𝑙 @ 𝑇; 𝑈
̂=𝑈 ̂𝑙 @ 𝑇; 𝐻
̂=𝐻 ̂𝑙 @ 𝑇.
The conditions that characterize liquid region are summarized in the figure below:
For details of looking at thermodynamic table, students are encouraged to look at the following texts:
 Sonntag, Richard E., Claus Borgnakke, and Gordon J. Van Wylen. Fundamentals of
Thermodynamics. 8th ed. Wiley-India edition.
 Çengel, Y. A., & Boles, M. A. (2015). Thermodynamics: An engineering approach.: 8th ed.
McGraw-Hill
Important note about Reference state:

Recall that we can never know the absolute values of specific internal energy and specific enthalpy for a
species at a given state. Fortunately, the absolute values of specific enthalpy and internal energy are never
required. We only need to know the changes in specific enthalpy and internal energy that the system
undergoes in a process (i.e. between initial and final states). These changes can be determined
experimentally. We can therefore choose an arbitrary reference state for a species and determine:
∆𝑈̂=𝑈 ̂− 𝑈 ̂𝑟𝑒𝑓
for the transition from reference state to a series of other states. If we set
̂𝑟𝑒𝑓 = 0 ⇒ 𝑈
𝑈 ̂ = ∆𝑈 ̂
for a specified state is the specific internal energy at that state relative to the reference state.
The values reported in thermodynamic tables (e.g steam tables) are generated using the above concept of
reference state. The reference state in steam tables given above is chosen as liquid water at triple point i.e
(H2O (l, 0.01oC, 0.00611 bar)) and accordingly:
𝑈̂ = 0 at this state (see row-1 and coulmn-5 of table-1)
𝑚3
specific enthalpy can be evaluated as: 𝐻 ̂=𝑈 ̂ + 𝑃𝑉̂ = 0 + 0.611 (kPa) × 0.001( ) ≈ 0
𝑘𝑔
All the values reported in steam tables are then given relative to this reference state. For example,
̂ = 2660.0 kJ/kg in Table-3 above at 𝑃 = 0.05 MPa, 𝑇 = 200℃
𝑈
does not mean that the absolute specific internal energy at this state is 2660 kJ/kg. It means that change in
specific internal energy in taking water from H2O (l, 0.01oC, 0.00611 bar) to H2O (v, 200oC, 0.05 MPa) is
2660.0 kJ/kg. Corresponding specific enthalpy can be determined as:
𝑚3
̂ ̂ ̂
𝐻 = 𝑈 + 𝑃𝑉 = 2660 + 50 (kPa) × 4.3562 ( ) = 2877.81 kJ/kg
𝑘𝑔
Problem 1: Fill out the following table for water:

Solution: Note that in each row, two independent intensive properties are given  we can find all other
properties.

Row-1: 𝑃 = 200 kPa, 𝑥 = 0.7.

since 0 ≤ 𝑥 ≤ 1 ⇒ liquid-vapor mixture

𝑇 = 𝑇𝑠𝑎𝑡 @𝑃 = 200 kPa = 120.23℃ (from steam tables i.e thermodynamic table for water)

̂ = ℎ = (𝐻
𝐻 ̂𝑙 + 𝑥𝐻
̂𝑙𝑣 ) @ 𝑃 = 200 kPa

̂ = 504.7 + 0.7 × 2201.7 = 2045.89 kJ/kg

𝐻

̂ = 1800 kJ/kg
Row-2: 𝑇 = 140℃, 𝐻

̂𝑙 (= 589.10) < 𝐻
Note from steam tables that at 𝑇 = 140℃, 𝐻 ̂ (= 1800 given) < 𝐻
̂𝑣 (= 2733.1) ⇒
liquid-vapor mixture.

Thus, 𝑃 = 𝑃𝑠𝑎𝑡 @ 𝑇 = 140℃ = 361.38 kPa

̂ = 1800 = (𝐻
𝐻 ̂𝑙 + 𝑥𝐻
̂𝑙𝑣 ) = 589.10 + 𝑥 × 2144.0

𝑥 = 0.565

Row-3: 𝑃 = 950 kPa, 𝑥 = 0

𝑥 = 0 ⇒ saturated liquid ⇒𝑇 = 𝑇𝑠𝑎𝑡 @𝑃 = 950 kPa = 177.6

̂= 𝐻
𝐻 ̂𝑙 @𝑃 𝑜𝑟 𝑇 (since it is saturated not compressed liquid) = 753.05 kJ/kg

̂= 𝐻
Note that if the state was compressed liquid then we would have taken 𝐻 ̂𝑙 @𝑇 rather than at P.

Row-4: 𝑇 = 80℃, 𝑃 = 500 kPa

Note 𝑃𝑠𝑎𝑡 = 473.6 kPa @ 𝑇 = 80℃ ⇒ 𝑃 > 𝑃𝑠𝑎𝑡 ⇒ compressed liquid

 ̂=𝐻
⇒𝐻 ̂𝑙 @𝑇 = 80℃ = 334.92kJ/kg and 𝑥 is not defined

̂ = 3190 kJ/kg
Row-5: 𝑃 = 800 kPa, 𝐻

̂> 𝐻
Since, 𝐻 ̂𝑣 (= 2767.3 kJ/kg) ⇒ superheated vapor

Look at tables for vapor region at 𝑃 = 800 kPa. A snapshot of tables in superheated region is shown
below:

Note the marked column for enthalpy for tables corresponding to P = 8 bar = 800 kPa. The given enthalpy
lies in between the enthalpies marked with curvy brackets. Thus, we have to interpolate in between these
two to determine temperature (or entropy or internal energy etc).

3267.07 − 3161.68 3267.07 − 3190

= ⇒ 𝑇 = 363.4℃
400 − 350 400 − 𝑇
Problem 2: 400 kg/h of steam enters a turbine at 45atm and 470℃ at a velocity of 60 m/s. The steam
expands in the turbine and delivers a work at a rate of 65 kW and leaves the turbine at a velocity of 350
m/s at a point 10 m below the inlet point at atmospheric pressure. The heat loss from the turbine is
estimated to be 12 kW. Calculate the specific enthalpy change associated with the process and the
temperature at which steam leaves the turbine.
Solution: Note that it is the same problem given in previous unit. The only change is to calculate the exit
temperature. The solution remains identical until calculation of enthalpy chnage.
Since, inlet state is known (470℃, 45𝑎𝑡𝑚) ⇒ 𝐻 ̂𝑖𝑛 can be determined using steam tables
As we know change in enthalpy, we can determine exit enthalpy. This implies exit state can be
determined (1𝑎𝑡𝑚, 𝐻 ̂𝑒𝑥𝑖𝑡 ).

System: Steam present in turbine at any given instant of time.

Open system ⇒ 𝑄̇ − 𝑊̇ = ∆𝐻̇ + ∆𝐸̇𝑘 + ∆𝐸̇𝑝

𝑄̇ = −12 kW (negative becuase heat is lost)

𝑊̇𝑠 = 65 kW (positive becuase work is done by the expanding steam)

1 2
∆𝐸̇𝑘 = 2
𝑚̇(𝑢𝑜𝑢𝑡 − 𝑢𝑖𝑛 )
2
400
𝑚̇ = kg/s = 0.1111 kg/s
3600

𝑢𝑜𝑢𝑡 = 350 m/s, 𝑢𝑖𝑛 = 60 m/s

∆𝐸̇𝑘 = 6605.6 J/s = 6.5056 kW

∆𝐸̇𝑝 = 𝑚̇𝑔(𝑧2 − 𝑧1 ) = 0.1111 × 9.8 × (−10 − 0) = 10.9 J/s = −1.09 × 10−2 kW

⇒ ∆𝐻̇ = 𝑄̇ − 𝑊̇ − ∆𝐸̇𝑘 − ∆𝐸̇𝑝 = −12 − 65 − 6.5 + 1.09 × 10−2 = −83.5 kW

83.5
̂= −
specific enthalpy change = ∆𝐻 = −751.5 kJ/kg
0.1111

Now, inlet state information known is 𝑃 = 45 𝑎𝑡𝑚 = 4500 kPa, 𝑇 = 470℃

 ̂𝑖𝑛
3439.51 − 3323.23 3439.51 − 𝐻
⇒ = (from steam table corresponding to P=45 atm)
500 − 450 500 − 470
̂𝑖𝑛 = 3369.74 kJ/kg
⇒𝐻

̂= 𝐻
∆𝐻 ̂𝑜𝑢𝑡 − 𝐻
̂𝑖𝑛 ⇒ −751.5 = 𝐻
̂𝑜𝑢𝑡 − 3369.74

̂𝑜𝑢𝑡 = 2618.24 kJ/kg

𝐻

Exit state (1𝑎𝑡𝑚 ≈ 100 kPa, 2618.24 kJ/kg)

̂𝑣 @ 100 kPa = 2675.4 kJ/kg > 2618.24 kJ/kg ⇒ liquid-vapor saturated mixture
𝐻

Thus, 𝑇 = 𝑇𝑠𝑎𝑡 @ 𝑃 = 100℃.

Note that we can as well calculate quality by using 𝐻 ̂ 𝑙 + 𝑥𝐻

̂ = (𝐻 ̂𝑙𝑣 )
Problem 3: 400 kg/h of steam enters a turbine at 45atm and 470℃ at a velocity of 60 m/s. The steam
expands in the turbine and delivers the work and saturated steam leaves the turbine at a velocity of 350
m/s at a point 10 m below the inlet point at atmospheric pressure. The heat loss from the turbine is
estimated to be 12 kW. Calculate the work delivered by the turbine.

400 kg/h 400 kg/h, 1atm , sat'd 350 m/s

45 atm, 470℃, 10 m below entry point.
60m/s

𝑄̇ = −12 𝑘𝑊, 𝑊̇𝑠 =? W

Open system ⇒ 𝑄̇ − 𝑊̇ = ∆𝐻̇ + ∆𝐸̇𝑘 + ∆𝐸̇𝑝

1 2
∆𝐸̇𝑘 = 2
𝑚̇(𝑢𝑜𝑢𝑡 − 𝑢𝑖𝑛 )
2
400
𝑚̇ = kg/s = 0.1111 kg/s
3600

𝑢𝑜𝑢𝑡 = 350 m/s, 𝑢𝑖𝑛 = 60 m/s

∆𝐸̇𝑘 = 6605.6 J/s = 6.5056 kW

∆𝐸̇𝑝 = 𝑚̇𝑔(𝑧2 − 𝑧1 ) = 0.1111 × 9.8 × (−10 − 0) = 10.9 J/s = −1.09 × 10−2 kW

400
∆𝐻̇ = 𝑚̇(𝐻
̂𝑜𝑢𝑡 − 𝐻
̂𝑖𝑛 ) = × (2675.4 − 3369.74) = −77.15 kJ/s
3600
𝑊̇ = 𝑄̇ − ∆𝐻̇ − ∆𝐸̇𝑘 − ∆𝐸̇𝑝 = −12 + 77.15 − 6.5 + 0.01 = +58.65 kW
 Fundamentals of Energy Balances
(Calculation of enthalpy and internal energy changes for different processes)

We discussed determination of enthalpies and internal energies for a pure substance at a given state using
thermodynamic tables in the previous unit. We continue with determination of enthalpy and internal
energy changes in this unit but with the help of mathematical relations. We discuss the calculations of
internal energy and enthalpy changes associated with five types of processes, namely:
1. Changes in pressure at constant temperature and state of aggregation.
2. Changes in temperature at constant pressure and state of aggregation.
3. Phase changes at constant temperature and pressure (melting, vaporization, solidifying etc.)
4. Mixing of two liquids or dissolving of solid or gas in a liquid at constant temperature and
pressure.
5. Chemical reaction at constant temperature and pressure.
We will restrict ourselves to the discussion of first three processes in this unit, fourth process and fifth
process will be discussed in next module. Once we know how to calculate specific internal energy and
specific enthalpy changes for these five processes, we can calculate ∆𝑈 ̂ and ∆𝐻̂ for any process by using
̂ 𝑎𝑛𝑑 𝐻
the fact that 𝑈 ̂ are state properties and hence, depends only on final and initial states.
As an example, consider a process in which cyclo-hexane vapors at 180℃ and 5 atm is converted to solid
cyclo-hexane at 1℃ and 1 atm. We wish to calculate the enthalpy (or internal energy) change for this
process in absence of thermodynamic tables for cyclo-hexane. The given process is:
̂
∆𝐻
CH(v,180℃,5 atm) → CH(s,1℃,1 atm)
̂
In order to calculate ∆𝐻, we construct a hypothetical path in which initial and final states are same as in
the actual process. A possible path is shown in the figure below:
̂1
∆𝐻 ̂2
∆𝐻 ̂3
∆𝐻
CH(v,180℃,5 atm) → CH(v,180℃,1 atm) → CH(v,80.7℃,1 atm) → CH(l,80.7℃,1 atm)
̂4
∆𝐻 ̂5
∆𝐻 ̂6
∆𝐻
→ CH(l,6.7℃,1 atm) → CH(s,6.7℃,1 atm) → CH(s,1℃,1 atm)
Note that we have used the fact that normal freezing point of liquid phenol is 6.7 ℃ and normal
condensation point (i.e condensation point at 1 atm) is 80.7℃. Based on this hypothetical path, the
enthalpy change is:
∆𝐻̂ = ∆𝐻 ̂1 + ∆𝐻 ̂2 + ∆𝐻 ̂3 + ∆𝐻 ̂4 + ∆𝐻̂5 + ∆𝐻 ̂6
Note that first step is type-1 process, 2nd is type-2, 3rd is type-3, 4th is type-2, 5th is type-3, and 6th is
type-2. Let us now discuss calculation of ∆𝐻 ̂ and ∆𝑈̂ for type 1-3 processes.
Changes in pressure at constant temperature and phase (Type-1 process):
The experimental observations demonstrate that the internal energy is nearly independent of pressure for
solids and liquids (in a manner similar to specific volume: Note liquid and solid materials do not change
volume on applying pressure ⇒ ∆𝑉̂ = 0). The specific internal energy is a strong function of temperature,
phase and composition. Thus, for pressure changes at constant phase and temperature: ∆𝑈 ̂ ≈ 0.
∆𝐻̂ = ∆(𝑈̂ + 𝑃𝑉̂ ) = ∆𝑈̂ + 𝑃∆𝑉̂ + 𝑉̂ ∆𝑃 ≈ 0 + 0 + 𝑉̂ ∆𝑃 ≈ 𝑉̂ ∆𝑃
∆𝐻̂ ≈̂𝑉 ∆𝑃
For ideal gases:
𝑈̂=𝑈 ̂(𝑇)and 𝐻̂=𝑈 ̂ + 𝑃𝑉̂ = 𝑈̂ + 𝑅𝑇 = 𝐻 ̂ (𝑇) ⇒ ∆𝑈 ̂ = ∆𝐻 ̂=0
For gases which are far from ideal behavior, both internal energy and enthalpy are functions of
temperature and pressure, thus, one must use thermodynamic tables or thermodynamic correlations.
While in the present course we do not present correlations, the students are referred to the following
reference as a source for such thermodynamic correlations:
R.C. Reid, J. H. Prausnitz, and B. E. Poling, The properties of gases and liquids, 4th edition, McGraw
Hill, New-York, 1987.
In the present course we will either use tables or assume ideal gas behavior.
Change in temperature at constant pressure and phase (Type-2 process)
We make use of specific heat definitions to calculate internal energy and enthalpy changes. The specific
heat capacity at constant volume is defined as:
𝜕𝑈 ̂
𝐶𝑣 (𝑇) = ( )
𝜕𝑇 𝑉̂
Thus, for a change in temperature from T1 to T2 at constant volume:
𝑇2

̂ = ∫ 𝐶𝑣 (𝑇)𝑑𝑇
∆𝑈
𝑇1
For a change from (T1, V1) to (T2, V2):
̂
∆𝑈1 2 ̂
∆𝑈
(𝑇1 , 𝑉̂1 ) → (𝑇1 , 𝑉̂2 )→ (𝑇2 , 𝑉̂2 )
∆𝑈̂ = ∆𝑈
̂1 + ∆𝑈 ̂2
Internal energy depends only on temperature for ideal gases and for solids, and liquids (to a good
̂1 can be taken as zero for all substances except non-ideal gases. Thus,
approximation), thus, ∆𝑈
𝑇2

̂ = ∆𝑈
∆𝑈 ̂2 = ∫ 𝐶𝑣 (𝑇)𝑑𝑇
𝑇1
The above expression is exact for ideal gases, good approximation for solid and liquid, and valid for non-
ideal gases only if volume is constant.
For calculation of enthalpy changes we use specific heat capacity at constant pressure:
𝜕𝐻 ̂
𝐶𝑝 (𝑇) = ( )
𝜕𝑇 𝑃
For a change of temperature at constant pressure:
𝑇2

̂ = ∫ 𝐶𝑝 (𝑇)𝑑𝑇
∆𝐻
𝑇1
̂
∆𝐻 ̂1
∆𝐻 ̂2
∆𝐻
For a process (𝑇1 , 𝑃1 ) → (𝑇2 , 𝑃2 ) ≡ (𝑇1 , 𝑃1 ) → (𝑇1 , 𝑃2 )→ (𝑇2 , 𝑃2 )
̂ = ∆𝐻
∆𝐻 ̂1 + ∆𝐻̂2
For ideal gases:
𝑇2

̂1 = 0 ⇒ ∆𝐻
∆𝐻 ̂ = ∫ 𝐶𝑝 (𝑇)𝑑𝑇
𝑇1
For non-ideal gases, the above expression holds only and only if pressure is constant (otherwise use
correlations or thermodynamic tables)
For solids and liquids:
 𝑇2

̂1 = 𝑉̂ ∆𝑃 ⇒ ∆𝐻
∆𝐻 ̂ = 𝑉̂ ∆𝑃 + ∫ 𝐶𝑝 (𝑇)𝑑𝑇
𝑇1
Usually, if changes in pressure are not large, the 𝑉̂ ∆𝑃 term is small relative to the integral term and is
neglected.
Note about specific heat capacities:
Both specific heat capacity at constant volume and constant pressure are functions of temperature. The
expression for specific heat at constant pressure is given as:
𝐶𝑝 = 𝑎 + 𝑏𝑇 + 𝑐𝑇 2 + 𝑑𝑇 3 where 𝑎, 𝑏, 𝑐, 𝑑 are constants
For example,
𝑎 = 0.02900, 𝑏 = 0.2199 × 10−5 , 𝑐 = 0.5723 × 10−8 , 𝑑 = −2.871 × 10−12 for nitrogen gas
For ideal gases:
𝐶𝑝 − 𝐶𝑣 = 𝑅
For solids and liquids
𝐶𝑝 ≈ 𝐶𝑣
Refer Table B.2, Appendix B for values of a, b, c, d for different substances in Richard M. Felder, and
Ronald W. Rousseau, Elementary principles of chemical processes, 2009, 3rd edition, Wiley India.
Note about calculation of enthalpy or internal energy changes for a mixture:
For calculating enthalpy or internal energy changes associated with a change in temperature undergone by
a mixture of species:
1. For a mixture of gases or liquids, calculate total enthalpy (or internal energy) change as the sum
of enthalpy changes for each pure component that constitutes the mixture. This procedure means
that we are neglecting any change associated with mixing process which is valid for ideal gases
and good approximation for similar liquids (like pentane and hexane, benzene and toluene etc).
However, this approximation will not work if we mix nitric acid and water for which we know
from experience that heat is released when acid and water are mixed. We will discuss accounting
of such mixing effects in next unit.
2. For highly dilute solution of solids or gases in liquid, we neglect enthalpy change for solute.
3. If composition of mixture is known, we can estimate the specific heat capacity of mixture as:
𝐶𝑝𝑚𝑖𝑥 = ∑𝑦𝑖 𝐶𝑝𝑖 (𝑇);
where 𝑦𝑖 = mole/mass fraction depending on the units in which 𝐶𝑝𝑖 is given
Phase change operations (Type-3 process)
In this section, we are referring to processes like vaporization, condensation, melting, solidification, and
sublimation. The specific enthalpy change associated with transition of a substance from one phase to
another at constant temperature and pressure is known as latent heat of the corresponding phase change.
Two most commonly encountered phase change operations are melting (reverse is solidification) and
vaporization (reverse is condensation). The definitions of latent heats for these two processes are:
Heat of melting (or fusion ∆𝑯 ̂ 𝒎 (𝑻, 𝑷)) is the change in specific enthalpy when a solid species is
transformed to liquid phase at constant temperature and pressure. Heat of solidification accordingly will
be negative of heat of melting.
Heat of vaporization (∆𝑯 ̂ 𝒗 (𝑻, 𝑷)) is the change in specific enthalpy when a liquid species is transformed
to vapor phase at constant temperature and pressure. Heat of condensation will be negative of heat of
vaporization ∆𝑯 ̂ 𝒗 (𝑻, 𝑷) = −∆𝑯 ̂ 𝒄 (𝑻, 𝑷).
The values of heat of melting and heat of vaporization at normal melting and boiling point (i.e. at 1 atm)
respectively, for several species are reported in Table B.1 in appendix B of Richard M. Felder, and
Ronald W. Rousseau, Elementary principles of chemical processes, 2009, 3rd edition, Wiley India.
Let us focus on heat on vaporization and the discussion that follows is equally applicable for heat of
melting as well. We expect specific enthalpy of vapor will be greater than specific enthalpy of liquid for
any species at same temperature and pressure. For example, we expect 𝐻 ̂𝑣𝑎𝑝𝑜𝑟 > 𝐻̂𝑙𝑖𝑞𝑢𝑖𝑑 for water at
100℃ and 1 atm pressure. This is because heat energy must be supplied to the liquid phase to overcome
the strong attractive forces between molecules in liquid state so that the molecules move apart and finally
reaches vapor state. This heat cause internal energy to increase and hence enthalpy also increases (in fact,
to a greater extent because 𝐻 ̂=𝑈 ̂ + 𝑃𝑉̂ and specific volume in vapor phase becomes significantly
higher). Also recall that for a pure substance at a given pressure, the phase change occurs at constant
temperature (or temperature and pressure are dependent properties for phase change operations). Thus,
∆𝐻̂𝑣 (𝑇, 𝑃) = 𝐻̂𝑣 − 𝐻 ̂𝑙 = 𝐻̂𝑙𝑣 ; where 𝐻̂𝑣 and 𝐻
̂𝑙 are enthalpies in saturated states
Thus, from steam tables, latent heat of vaporization for water:
∆𝐻 ̂𝑣 (100℃, 1 𝑎𝑡𝑚) = 𝐻 ̂𝑣 − 𝐻̂𝑙 = 2675.6 − 419.17 = 2256.4 kJ/kg
Further, latent heat of phase change depends strongly on temperature but hardly varies with pressure. This
is clear from the following data:
∆𝐻̂𝑣 (25℃, 23 𝑚𝑚 𝐻𝑔) = 2442.5 kJ/kg and ∆𝐻 ̂𝑣 (25℃, 760 𝑚𝑚 𝐻𝑔) = 2442.3 kJ/kg
For calculation of ∆𝑈 ̂ for processes involving phase change:
∆𝑈̂ = ∆𝐻̂ − ∆(𝑃𝑉̂ )
Again for melting which involves transition from solid state to liquid state, changes in PV type of term
will be negligible and hence:
∆𝑈̂ ̂
𝑚 = ∆𝐻𝑚
For vaporization process, PV type term for vapor will be significantly larger than PV type term for liquid
and hence:
∆𝑈̂𝑣 = ∆𝐻 ̂𝑣 − [∆(𝑃𝑉̂ )] ≈ ∆𝐻̂𝑣 − 𝑅𝑇 (assuming ideal vapor; may not be good approximation)
𝑣𝑎𝑝𝑜𝑟

Correlations for latent heats:

Trouton's rule:
̂𝑣 (kJ/mol) = 0.88𝑇𝑏 (𝐾) (non-polar liquids)
∆𝐻
∆𝐻̂𝑣 (kJ/mol) = 0.109𝑇𝑏 (𝐾) (water, low-molecular weight alcohols)
Where Tb is the normal boiling point of liquid. The accuracy of the formula is with 30%.
Chen's rule:
𝑇
[𝑇𝑏 (0.0331 ( 𝑇𝑏 ) − 0.0327 + 0.0297 log10 𝑃𝑐 )]
̂𝑣 (kJ/mol) = 𝑐
∆𝐻
𝑇
[1.07 − 𝑇𝑏 ]
𝑐
Where Tb and Tc are normal boiling point and critical temperature in Kelvin and Pc is the critical pressure
in atmospheres.
A correlation for approximating a standard heat of fusion is:
∆𝐻̂𝑚 (kJ/mol) = 0.0092𝑇𝑚 (𝐾) (metallic elements)
̂𝑚 (kJ/mol) = 0.0025𝑇𝑚 (𝐾) (inorganic compounds)
∆𝐻
∆𝐻̂𝑚 (kJ/mol) = 0.050𝑇𝑚 (𝐾) (organic compounds)
Watson' correlation: used for approximating heat of vaporization at second temperature from a known
value at given temperature T1:
𝑇𝑐 − 𝑇2 0.38
̂ ̂
∆𝐻𝑣 (𝑇2 ) = ∆𝐻𝑣 (𝑇1 ) ( )
𝑇𝑐 − 𝑇1
Problem-1: A stream of nitrogen flows in a pipe at a rate of 120 mol/min. The stream is heated using an
oil bath. Nitrogen enters the oil bath section at 20oC and leaves at 90oC. Calculate the amount of heat
transferred to the nitrogen. ( 𝐶𝑝 = 𝑎 + 𝑏𝑇 + 𝑐𝑇 2 + 𝑑𝑇 3 ; 𝑎 = 0.02900, 𝑏 = 0.2199 × 10−5 , 𝑐 =
0.5723 × 10−8 , 𝑑 = −2.871 × 10−12 )
Problem-2: Calculate the amount of heat transferred to cool nitrogen from 100oC to 20oC which is kept in
a 5 liter flask at an initial pressure of 250 kPa.
Problem-3: The enthalpy of water vapor at 200 kPa and 200oC is reported as 2870.46 kJ/kg in steam
tables with reference state as liquid water at triple point. Using latent heat of vaporization at normal
boiling point and expression of specific heat capacities for water, determine specific enthalpy at 200 kPa
and 200oC.
𝐶𝑝 (𝐻2 𝑂(𝑙)) = 4.188 kJ/kg ℃;
𝐶𝑝 (kJ/mol k) = 0.03346 + 0.6880 × 10−5 𝑇 + 0.7604 × 10−8 𝑇 2 − 3.593 × 10−12 𝑇 3 for water vapor
Problem-4: Determine latent heat of vaporization at (i) (25oC, 1atm), (ii) (25oC, 10 atm), and (iii) (50oC,
1atm).
 Fundamentals of Energy Balances
Energy Balance calculation procedure

Following steps are followed for performing energy balance calculations for all problems:
1. Draw a completely labeled flowchart. The labeling of each stream must mention work transfer,
heat transfer, temperature, pressure, and phase of each component in addition to the variables
required for material balance calculations (flow rates and compositions).
2. Solve the material balances as much as possible
3. Identify the type of system (open or closed) and accordingly write down the appropriate form of
energy balance equation. Remove terms that are zero or negligible for the given process. For
example, kinetic and potential energy terms are often neglected for closed systems. The work
term is neglected if volume remains constant for a closed system. However, work may be present
if the system involves moving parts like mixer, impellers etc. Similarly for open system, changes
in kinetic and potential energies are often neglected unless the velocities involved are very high
(for KE) and change in elevation is significant (for PE).
4. Expand each term of energy balance. This step will become clear as we take up an example in the
following discussion.
5. Choose a reference state. This is one of the most important steps in performing energy balance
calculations. The reference state must be chosen for all species present in the system. If
thermodynamic tables are available for a species, choose the reference state which is used to
generate the table; otherwise, choose one of the inlet or outlet states as the reference state for the
species. The procedure will be explained in an example problem below.
6. Calculate all the terms appearing in expanded energy balance equation. This will mostly involve
calculations of enthalpies and internal energies relative to the reference state chosen in step-4.
7. Solve the energy balance (simultaneously with material balance if required) for whichever
variable is unknown (often heat transfer rate for open system or amount of heat for closed
system).
In the following we give a sample energy balance problem to illustrate all the steps given above.

A gas-vapor mixture of pentane (50 mole %), n-hexane (30 mole %), and nitrogen (20 mole %) is at 65oC
and 1.75 atm is fed at a rate of 100 mol/min to a condenser. The vapor and liquid stream in equilibrium
with each other exits the condenser at 30oC and P atm. The liquid stream contains 35% pentane.
Determine the rate of heat removal from the condenser. Thermodynamic table for nitrogen are available
(see Table B.8 in Appendix B Richard M. Felder, and Ronald W. Rousseau, Elementary principles of
chemical processes, 2009, 3rd edition, Wiley India). Specific heat capacity expressions are available for
n-pentane and n-hexane.
Step-1: Draw flowchart: (let P denote pentane, H denote hexane)

Step-2: Solve the material balance as much as possible. In this problem we will be able to solve the
material balance completely.
𝐷𝑂𝐹 = 5(𝑛𝑣 , 𝑛𝑙 , 𝑦𝑝 , 𝑦𝐻 , 𝑃) − 3 material bal − 2 equilb relation (Raoult' s law)
Heat removal rate will then be solved using energy balance equation.
Equilibrium relations:
𝑥𝑃 𝑝𝑃∗ (30℃) = 𝑦𝑃 𝑃 for pentane
(1 − 𝑥𝑃 )𝑝𝐻∗ (30℃) = 𝑦𝐻 𝑃 for hexane
Using Antoine equation for determining vapor pressure of pentane and hexane (refer table B.4, Appendix
B in Richard M. Felder, and Ronald W. Rousseau, Elementary principles of chemical processes, 2009,
3rd edition, Wiley India.)
𝐵
log10 𝑝∗ = 𝐴 − ; 𝑇 𝑖𝑛 ℃ and 𝑝∗ 𝑖𝑛 𝑚𝑚 𝐻𝑔
𝑇+𝐶
For pentane:
𝐴 = 6.84471, 𝐵 = 1060.793, 𝐶 = 231.541
For hexane:
𝐴 = 6.88555, 𝐵 = 1175.817, 𝐶 = 224.867

𝑝𝑃∗ (30℃) = 614.86 𝑚𝑚 𝐻𝑔, 𝑝𝐻∗ (30℃) = 187.11 𝑚𝑚 𝐻𝑔

0.35 × 614.86 = 𝑦𝑃 𝑃
0.65 × 187.11 = 𝑦𝐻 𝑃
𝑦𝑃
⇒ = 1.769
𝑦𝐻
Total balance:
𝑛𝑣 + 𝑛𝑙 = 100
Pentane balance:
0.35𝑛𝑙 + 𝑦𝑃 𝑛𝑣 = 50
Nitrogen balance:
20
= 1 − 𝑦𝑃 − 𝑦𝐻
𝑛𝑣
Solving the above equations:
𝑛𝑣 = 28.09 mol/min; 𝑛𝑙 = 71.91mol/min;
𝑦𝑃 = 0.183 mol P/mol; 𝑦𝐻 = 0.104 mol P/mol
P from any of the above equilibrium relation:
0.35 × 614.86
𝑃= = 1175.96 𝑚𝑚 𝐻𝑔 = 1.55 𝑎𝑡𝑚
0.183
Step-3: The system is open system. Neglecting changes in KE and PE, we have:
 𝑄̇ − 𝑊̇ = ∆𝐻̇ + ∆𝐸̇𝑘 + ∆𝐸̇𝑝
𝑊̇ = 0, ∆𝐸̇𝑘 = ∆𝐸̇𝑝 = 0
𝑄̇ = ∆𝐻̇ = ∑ 𝑚̇𝑜𝑢𝑡 𝐻
̂𝑜𝑢𝑡 − ∑ 𝑚̇𝑖𝑛 𝐻
̂𝑖𝑛
𝑜𝑢𝑡 𝑖𝑛
Step-4: Expand each term of the energy balance.

̂𝑜𝑢𝑡 = 𝑛𝑣 𝑦𝑝 𝐻
∑ 𝑚̇𝑜𝑢𝑡 𝐻 ̂𝑃(𝑣,30℃,1.55𝑎𝑡𝑚) + 𝑛𝑣 𝑦𝐻 𝐻
̂𝐻(𝑣,30℃,1.55𝑎𝑡𝑚) + 𝑛𝑣 𝑦𝑁 𝐻
̂
2 𝑁2 (𝑣,,30℃,1.55𝑎𝑡𝑚)
𝑜𝑢𝑡
̂𝑃(𝑙,30℃,1.55𝑎𝑡𝑚) + 𝑛𝑙 × 0.65𝐻
+ 𝑛𝑙 × 0.35𝐻 ̂𝐻(𝑙,,30℃,1.55𝑎𝑡𝑚)
Note that summation is done over all the components in both exit streams and the phase, temperature and
pressure are mentioned in each enthalpy term while expanding the out sum terms.
Similarly for inlet stream:
̂𝑖𝑛 = 0.5 × 100 𝐻
∑ 𝑚̇𝑖𝑛 𝐻 ̂𝑃(𝑣,65℃,1.75𝑎𝑡𝑚) + 0.3 × 100 𝐻
̂𝐻(𝑣,65℃,1.75𝑎𝑡𝑚)
𝑖𝑛
+ 0.2 × 100̂ 𝐻𝑁2 (𝑣,65℃,1.75𝑎𝑡𝑚)
Step-5: Choose the reference state. Note that we have to choose reference state for all the components
present in the system. In the given problem, three components are present namely: pentane, hexane and
nitrogen. Since, thermodynamic tables are given for nitrogen (see table below), the reference state for
nitrogen will be taken as used in thermodynamic tables. The specific heat capacity expressions are
given for pentane and hexane, thus, we can choose reference state as per our convenience.
Reference state:
pentane(𝑣, 65℃, 1.75 𝑎𝑡𝑚); hexane(𝑣, 65℃, 1.75 𝑎𝑡𝑚); Nitrogen(𝑔, 25℃, 1𝑎𝑡𝑚)
The thermodynamic table for few select gases is given below:

𝐶𝑝 (kJ/mol K) = 𝑎 + 𝑏𝑇 + 𝑐𝑇 2 + 𝑑𝑇 3
For hexane vapor:
𝑎 = 0.13744, 𝑏 = 40.85 × 10−5 , 𝑐 = −23.92 × 10−8 , 𝑑 = 57.66 × 10−12
For pentane vapors:
𝑎 = 0.1148, 𝑏 = 34.09 × 10−5 , 𝑐 = −18.99 × 10−8 , 𝑑 = 42.26 × 10−12
For Hexane liquid:
𝐶𝑝 = 0.2163 kJ/mol K
For pentane liquid:
𝐶𝑝 (kJ/mol K) = 0.1554 + 43.68 × 10−5 𝑇
Step-6: Evaluation of all terms appearing in ∑𝑖𝑛 𝑚̇𝑖𝑛 𝐻 ̂𝑖𝑛 and ∑𝑜𝑢𝑡 𝑚̇𝑜𝑢𝑡 𝐻
̂𝑜𝑢𝑡 . This specifically implies
̂ terms.
calculation of all 𝐻
As per the choices of reference state:
̂𝑁 (𝑔,25℃,1𝑎𝑡𝑚) = 0; 𝐻
𝐻 ̂𝑃(𝑣,65℃,1.75𝑎𝑡𝑚) = 0; 𝐻𝐻(𝑣,65℃,1.75𝑎𝑡𝑚) = 0
2

̂𝑜𝑢𝑡 = 𝑛𝑣 𝑦𝑝 𝐻
∑ 𝑚̇𝑜𝑢𝑡 𝐻 ̂𝑃(𝑣,30℃,1.55𝑎𝑡𝑚) + 𝑛𝑣 𝑦𝐻 𝐻
̂𝐻(𝑣,30℃,1.55𝑎𝑡𝑚) + 𝑛𝑣 𝑦𝑁 𝐻
̂
2 𝑁2 (𝑣,,30℃,1.55𝑎𝑡𝑚)
𝑜𝑢𝑡
̂𝑃(𝑙,30℃,1.55𝑎𝑡𝑚) + 𝑛𝑙 × 0.65𝐻
+ 𝑛𝑙 × 0.35𝐻 ̂𝐻(𝑙,,30℃,1.55𝑎𝑡𝑚)

̂𝑃(𝑣,30℃,1.55𝑎𝑡𝑚) implies a change of state from 𝑃(𝑣, 65℃, 1.75 𝑎𝑡𝑚) 𝑡𝑜 𝑃(𝑣, 30℃, 1.55𝑎𝑡𝑚)
𝐻
30℃
̂𝑃(𝑣,30℃,1.55𝑎𝑡𝑚) = ∆𝐻
𝐻 ̂ for P(v, 65℃,1.75 atm) to P(v,65℃,1.55atm) + ∫ 𝐶𝑝 𝑑𝑇
65℃
Assuming that pentane vapors behave ideally, the enthalpy change for first term will be zero.
30℃
̂𝑃(𝑣,30℃,1.55𝑎𝑡𝑚) = 0 + ∫
𝐻 𝐶𝑝 𝑑𝑇 = −4.681 kJ/mol
65℃
Following similar procedure (refer previous unit):
30℃
̂𝐻(𝑣,30℃,1.55𝑎𝑡𝑚) = ∫
𝐻 𝐶𝑝 𝑑𝑇 = −5.470 kJ/mol
65℃

̂𝑁 (𝑣,,30℃,1.55𝑎𝑡𝑚) = 0.146 kJ/mol

𝐻 2

(using thermodynamic tables and neglecting pressure changes)

̂𝑃(𝑙,30℃,1.55𝑎𝑡𝑚) =?
𝐻

Construct hypothetical path:

𝑃(𝑣, 65℃, 1.75 𝑎𝑡𝑚) → 𝑃(𝑣, 65℃, 1𝑎𝑡𝑚) → 𝑃(𝑣, 36.07℃, 1𝑎𝑡𝑚) → 𝑃(𝑙, 36.07℃, 1𝑎𝑡𝑚)
→ 𝑃(𝑙, 30℃, 1𝑎𝑡𝑚) → 𝑃(𝑙, 30℃, 1.55𝑎𝑡𝑚)

Since we are assuming ideal gas behavior, the changes in pressure in vapor phase will not cause any
enthalpy change (hence zero for hypothetical path-1 above). Further, in the last step (or last hypothetical
process path), the change in enthalpy will be 𝑉̂ ∆𝑃 whose contribution usually remains insignificant as
specific volume values are generally low for liquids. Thus,
36.07℃ 30℃
̂𝑃(𝑙,30℃,1.55𝑎𝑡𝑚) = 0 + ∫
𝐻 (𝐶𝑝 ) ̂𝑣 ) + ∫
𝑑𝑇 + (−∆𝐻 (𝐶𝑝 ) 𝑑𝑇 + 𝑉̂ ∆𝑃(≈ 0)
𝑃
65℃ 𝑃(𝑣𝑎𝑝𝑜𝑟) 36.07℃ 𝑃(𝑙𝑖𝑞)

̂𝑣 ) @normal boiling point = 25.77 kJ/mol

(∆𝐻 𝑃

̂𝑃(𝑙,30℃,1.55𝑎𝑡𝑚) = −4.681 − 25.77 − 1.025 = −31.476 kJ/mol

𝐻

Similarly,
 ̂𝐻(𝑙,,30℃,1.55𝑎𝑡𝑚) =?
𝐻

𝐻(𝑣, 65℃, 1.75 𝑎𝑡𝑚) → 𝐻(𝑣, 65℃, 1𝑎𝑡𝑚) → 𝐻(𝑣, 68.74℃, 1𝑎𝑡𝑚) → 𝐻(𝑙, 68.74℃, 1𝑎𝑡𝑚)
→ 𝐻(𝑙, 30℃, 1𝑎𝑡𝑚) → 𝐻(𝑙, 30℃, 1.55𝑎𝑡𝑚)
68.74℃ 30℃
̂𝐻(𝑙,30℃,1.55𝑎𝑡𝑚) = 0 + ∫
𝐻 (𝐶𝑝 ) ̂𝑣 ) + ∫
𝑑𝑇 + (−∆𝐻 (𝐶𝑝 ) 𝑑𝑇 + 𝑉̂ ∆𝑃(≈ 0)
𝑃
65℃ 𝐻(𝑣𝑎𝑝𝑜𝑟) 68.74℃ 𝐻(𝑙𝑖𝑞)

̂𝑣 ) @normal boiling point= 68.74℃ = 28.85 kJ/mol

(∆𝐻 𝐻

̂𝐻(𝑙,30℃,1.55𝑎𝑡𝑚) = 0.616 − 28.85 − 8.379 = −36.613 kJ/mol

𝐻

̂𝑜𝑢𝑡 = 𝑛𝑣 𝑦𝑝 𝐻
∑ 𝑚̇𝑜𝑢𝑡 𝐻 ̂𝑃(𝑣,30℃,1.55𝑎𝑡𝑚) + 𝑛𝑣 𝑦𝐻 𝐻
̂𝐻(𝑣,30℃,1.55𝑎𝑡𝑚) + 𝑛𝑣 𝑦𝑁 𝐻
̂
2 𝑁2 (𝑣,,30℃,1.55𝑎𝑡𝑚)
𝑜𝑢𝑡
̂𝑃(𝑙,30℃,1.55𝑎𝑡𝑚) + 𝑛𝑙 × 0.65𝐻
+ 𝑛𝑙 × 0.35𝐻 ̂𝐻(𝑙,,30℃,1.55𝑎𝑡𝑚)
̂𝑜𝑢𝑡 = 28.09 × 0.183 × (−4.681) + 28.09 × 0.104 × (−5.470) + 28.09 × 0.713 × 0.146
∑ 𝑚̇𝑜𝑢𝑡 𝐻
𝑜𝑢𝑡
+ 71.91 × 0.35 × (−31.476) + 71.91 × 0.65 × (−36.613) = −70361.8 kJ/min
̂𝑖𝑛 = 0.5 × 100 𝐻
∑ 𝑚̇𝑖𝑛 𝐻 ̂𝑃(𝑣,65℃,1.75𝑎𝑡𝑚) + 0.3 × 100 𝐻
̂𝐻(𝑣,65℃,1.75𝑎𝑡𝑚)
𝑖𝑛
+ 0.2 × 100̂
𝐻𝑁2 (𝑣,65℃,1.75𝑎𝑡𝑚)

̂𝑖𝑛 = 0 + 0 + 20 × 1.168 = 23.36 kJ/min

∑ 𝑚̇𝑖𝑛 𝐻
𝑖𝑛

Step-7:

𝑄̇ = ∆𝐻̇ = ∑ 𝑚̇𝑜𝑢𝑡 𝐻
̂𝑜𝑢𝑡 − ∑ 𝑚̇𝑖𝑛 𝐻
̂𝑖𝑛 = −70385.16 kJ/min = −1173 kW
𝑜𝑢𝑡 𝑖𝑛
Problem 1: A solid fuel contains 4.7% H (not including the hydrogen in the coal moisture), 73 wt% C, 6.8% H2 O,
3.7% S and 11.8% ash. 50,000 lbm/h of fuel is burned in the power plant furnace with air 50% in excess
of that needed to oxidize all the carbon in the coal to CO2 . Both air and fuel are fed at 77 o F and 1 atm.
The solid residue from the furnace is found to contain 28.7 wt%C, 1.6% S and the balance ash. The sulfur
present in the fuel is oxidized in the furnace to SO2 (g). Of all the ash in the fuel, 30% emerges in the
solid residue and the balance is emitted with the stack gases as flu ash. The solid residue and stack gas
emerge from the furnace at 600o F. The heat of combustion of fuel at 77o F, assuming that water vapors
are produced as one of the combustion products, is -18000 Btu/lbm.

(a) Draw a completely labeled flowchart (No need to find degree of freedom). Calculate the mass flow
rates of all components in the stack gas and solid residue emerging from the furnace.
(b) Assuming that 40% of heat generated in the furnace is used to produce electricity, calculate the rate
of electricity generation in MW. Take heat capacity of solid furnace residue as 0.25 Btu/(lbm o F),
and heat capacity of fly ash present in stack gas as 0.185 Btu/(lbm o F). While calculating the heat
generated in the furnace, neglect the contribution of SO2 present in the stack gas.

Solution: (a)

0.73 × 50000 lbm C  1 lbmol C
50000 lbm coal/h ≡  12 lbm C = 3041.6 lbmol C/h
h
0.047 × 50000
≡ = 2350 lbmol H/h
1
0.037 × 50000
≡ = 57.8 lbmol S/h
32
0.068 × 50000
≡ = 188.9 lbmol H2 O/h
18
≡ 5900 lbmol ash/h

C + O2 → CO2 (50% excess air)

  
3041.6 lbmol C  1 lbmol O2  1 lbmol air 
n1 =  1 lbmol C  0.21 lbm O2  1.5 = 21725.7 lbmol air/h = 630045.3 lb air/h
h

30% condition, 0.30 × 5900 = 0.697 × m8 ⇒ m8 = 2539.5 lbm solid residue/h

Ash balance: 5900 = m2 + 0.697m8 ⇒ m2 = 4130 lbm ash/h
C balance:
50000 × 0.73 = 0.287m8 + 12n2 ⇒ n2 = 2980.9 lbmol CO2 /h = 1.31 × 105 lbm CO2 /h
H balance:
50000×0.047+(0.068×50000/18)×2 = 2n3 ⇒ n3 = 1363.9 lbmol H2 O/h = 24550.2 lbm H2 O/h
 S balance:
50000 × 0.037 = 0.016m8 + 32n4 ⇒ n4 = 56.5 lbmol SO2 /h = 3616 lbm SO2 /h
N balance: n6 = 17163.3 lbmol N2 /h = 480572.5 lbm N2 /h
O balance: (0.068 × 50000/18) + (0.21n1 ) × 2 = 2n2 + n3 + 2n4 + 2n5
⇒ n5 = 937.5 lbmol O2 /h = 30000 lbm O2 /h
(b) Reference: Coal components (C,H,S,H2 O, ash), air and all gases @ 77o F and 1 atm

Q̇ = ∆Ḣ
X X
= mcoal burned (∆Ĥc )coal + ne Ĥe − ni Ĥi
exit inlet

h
Q̇ = 50000(−18000) + n2 ĤCO (g, 600o F) + n3 ĤH O (g, 600o F) + n4 ĤSO (g, 600o F)
2 2 2
i
+n5 ĤO (g, 600o F) + n6 ĤN (g, 600o F) + n7 Ĥash(600o F)
2 2
h i
+m8 ĤSR(600o F) − 50000Ĥcoal(77o F, 1 atm) + n1 Ĥcoal(77o F, 1 atm)

Q̇ = −9 × 108 Btu/h + [2980.9 × 5293 + 1363.9 × 4359 + 0 + 937.5 × 3858 + 17163.3 × 3694
+4130 × 0.185(600 − 77)] + 2539.5 × 0.25(600 − 77) − [0 + 0]
= −8.062 × 108 Btu/h

0.40 × 8.062 × 108 Btu 

 
1J  1h 6
Power generated =  9.486 × 10−4 Btu  3600s = 94.43 J/s = 94.43MW

h
Problem-2: An air stream enters a condenser at 50o C and 1 atm with 2o C of superheat at a molar flow
rate of 100 mol/min. The air stream leaving the condenser is in equilibrium with the liquid condensate and
exits at a temperature and pressure of 20o C and 1 atm.
1. Draw and label a flowchart and perform a degree of freedom analysis to verify that all labeled
variables can be determined.Calculate the mass of water condensed per m3 of air fed to the condenser.
2. Calculate the amount of heat transferred in the above process.
5 8 12
C p , air ( kJ / mol )  0.02894  0.4147  10 T  0.3191  10 T  1.965  10 T
2 3

5 8 12
C p , H O ( v ) ( kJ / mol )  0.03346  0.688  10 T  0.7604  10 T  3.593  10 T
2 3

C p , H O ( l ) ( kJ / mol )  0.0754, H v , H O (100 C )  40.656kJ / mol ,

o

2 2

R  8.314 Pa.m / mol.K

3
Problem 3: A fuel gaseous mixture of methane (95 mol %) and balance ethane undergo combustion in a furnace with
20% excess air. The flue gas which do not contain unburned hydrocarbons or CO leaves the furnace at
1000 o C and 1.5 atm. The flue gases leaving the furnace pass through a well insulated heat exchanger to
preheat the air from 20 to 250 o C. Assuming a 100 mol/min of fuel gas mixture is fed to furnace.

(a) Calculate the required molar flow rate of air fed to the furnace. Calculate the molar flow rate and
composition of stack gas.
(b) Calculate the rate of heat transfer in the heat exchanger, and the temperature at which flue gas leaves
the heat exchanger.
(c) What would be the rate of heat transfer if the actual feed rate of flue gas were 450 SCMH?

Cp(CO2 ) = 0.0361; Cp(H2 O(v)) = 0.03346; Cp(O2 ) = 0.0291; Cp(N2 ) = 0.029 all in KJ/mol o C

Solution: (a) Let M and E denotes methane and ethane.

CH4 + 2O2 → CO2 + 2H2 O

C2 H6 + (7/2)O2 → 2CO2 + 3H2 O

Theoritical O2 = (95 × 2 + 5 × 3.5) = 207.5; given 20% excess air in feed

nO2 = 207.5 × 1.2 = 249 mol O2 /min nN2 = 3.76 × 249 = 936.24 mol N2 /min
nair = 1185.24 mol air/min
CO2 balance on furnace: n1 = 95 × 1 + 5 × 2 = 105 mol CO2 /min
H2 O balance: n2 = 95 × 2 + 5 × 3 = 205 mol H2 O/min
N2 balance: n4 = 936.24 mol N2 /min
O2 balance: n3 = 249 − (95 × 2 + 5 × 3.5) = 41.5 mol O2 /min

(b) Applying energy balance on air (in heat exchanger) (Reference: air @ 25o C, as given in thermodynamic
tables)

Q̇ = nair (Ĥout − Ĥin ) = nair (Ĥ250o C − Ĥ20o C ) = 1185.7(6.660 + 0.144) = 8067.5 kJ/min

Applying energy balance on stack gases (Reference: all gases @ 1000o C)

hX i hX i
Q̇ = ne Ĥe − ni Ĥi
Inlet heat (i.e., [2nd term] in RHS) is zero due to the choice of reference state.
" Z #
T Z T Z T Z T
= n1 Cp,CO2 dT + n2 Cp,H2 o dT + n3 Cp,O2 dT + n4 Cp,N2 dT − [0]
1000 1000 1000 1000

−8067.5 = (T − 1000)[105 × 0.0361 + 205 × 0.03346 + 41.5 × 0.0291 + 936.24 × 0.029]

⇒ T = 794.33o C
(c) No. of moles corresponding to 450 m3 (STP)/h

450m3 (STP) 
 
1kmol  1h
=  = 5.58 × 10−3 kmol/s = 5.58mol/s
h  22.4m3 (STP)  3600s

scale up factor = 5.58/100

5.58
Q̇new = × 8067.5 = 450.2kJ/min
100
 Energy Balances on Mixing and reactive processes
Energy Balances for reactive processes: Introduction

A typical energy balance problem involving reaction(s) is: A reaction A(l) + B(g)  C(g) + D(l) + heat
is carried out in a reactor as shown below:

Given flow rates and composition of all input and exit streams, calculate the amount of heat transfer rate
required to maintain reactor temperature at 120oC (or alternatively, if heat transfer rate is known,
determine the temperature of exit stream). However, before we discuss the methodology to solve such
energy balance problems, we introduce several terms that are frequently used in energy balances for
processes involving reactions.
Heat of reaction ∆𝑯 ̂ 𝒓 (𝑻, 𝑷): is defined as the enthalpy change associated with a process in which
stoichiometric quantities of reactant at some specified T and P react completely to form products at same
P and T. It is referred to as standard heat of reaction (∆𝐻̂𝑟° ) if (T,P) = (25oC, 1 atm). In order to clearly
understand heat of reaction, consider a reaction:
𝐶𝑎𝐶2 (𝑠) + 2 𝐻2 𝑂 (𝑙) → 𝐶𝑎(𝑂𝐻)2 (𝑠) + 𝐶2 𝐻2 (𝑔)
which is carried out as shown below:

∆𝐻 for reaction = ∆𝐻 ̂𝑟 (𝑇, 𝑃)

From experimental data, the heat of reaction for above reaction is:
∆𝐻 ̂𝑟 (25℃, 1 𝑎𝑡𝑚) = −125 kJ/mol
This implies that 125 kJ of heat is released when 1 mol of CaC2 reacts with 2 mol of water to give
Ca(OH)2 and C2H2 all at 25oC. Thus, the meaning of per mole in reporting heat of reaction implies:
−125 kJ −125 kJ −125 kJ
≡ =
1 𝑚𝑜𝑙 𝐶𝑎𝐶2 𝑐𝑜𝑛𝑠𝑢𝑚𝑒𝑑 2 𝑚𝑜𝑙 𝐻2 𝑂 𝑐𝑜𝑛𝑠𝑢𝑚𝑒𝑑 1 𝑚𝑜𝑙𝑒 𝐶𝑎(𝑂𝐻)2 𝑝𝑜𝑑𝑢𝑐𝑒𝑑
−125 kJ
=
1 𝑚𝑜𝑙𝑒 𝐶2 𝐻2 𝑝𝑟𝑜𝑑𝑢𝑐𝑒𝑑
For a general reaction:
∑𝜈𝑖 𝑆𝑖 ≡ 0; with heat of reaction ∆𝐻 ̂𝑟 (𝑇, 𝑃)
If 𝜁 is the extent of reaction, then enthalpy change associated with given extent of reaction (or
equivalently conversion) is
𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑖 𝑡ℎ 𝑠𝑝𝑒𝑐𝑖𝑒𝑠 𝑐𝑜𝑛𝑠𝑢𝑚𝑒𝑑 𝑜𝑟 𝑔𝑒𝑛𝑒𝑟𝑎𝑡𝑒𝑑
∆𝐻 = ∆𝐻̂𝑟 (𝑇, 𝑃) = 𝜁∆𝐻
̂𝑟 (𝑇, 𝑃)
|𝜈𝑖 |
Few observations related to heat of formation:
 Heat of reaction is negative for exothermic reaction and positive for endothermic reactions.
 Heat of reaction is nearly independent of pressure.
  Value of heat of reaction depends on how stoichiometric equation is written:
° (25℃)
2 𝐴(𝑙) + 𝐵(𝑔) → 𝐶(𝑔) + 𝐷(𝑙); ∆𝐻𝑟1 = −50 kJ/mol
° (25℃)
4 𝐴(𝑙) + 2𝐵(𝑔) → 2𝐶(𝑔) + 2𝐷(𝑙); ∆𝐻𝑟1 = −2 × 50 kJ/mol = 100 kJ/mol
 Heat of reaction also depends on phase of reactants and products. For example:
𝐶𝐻4 (𝑔) + 2𝑂2 (𝑔) → 𝐶𝑂2 (𝑔) + 2𝐻2 𝑂(𝑙); ∆𝐻 ̂𝑟1 (25℃) = −890.3 kJ/mol
𝐶𝐻4 (𝑔) + 2𝑂2 (𝑔) → 𝐶𝑂2 (𝑔) + 2𝐻2 𝑂(𝑣); ∆𝐻 ̂𝑟2 (25℃) = −802.3 kJ/mol
Note that the only difference between the two reactions is that water is formed as vapors in
second while it is formed as liquid in first reaction. The difference in heat of reaction is associated
with change in enthalpy corresponding to vaporization of two moles of water at 25oC. This can be
shown as follows:
∆𝐻̂𝑟1 (25℃) = 𝐻𝑝𝑑𝑡 − 𝐻𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠 = 𝐻 ̂𝐶𝑂 (𝑔) + 2𝐻 ̂𝐻 𝑂(𝑙) − 𝐻̂𝐶𝐻 (𝑔) − 2𝐻 ̂𝑂 (𝑔)
2 2 4 2
∆𝐻̂𝑟2 (25℃) = 𝐻𝑝𝑑𝑡 − 𝐻𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠 = 𝐻 ̂𝐶𝑂 (𝑔) + 2𝐻̂𝐻 𝑂(𝑣) − 𝐻 ̂𝐶𝐻 (𝑔) − 2𝐻 ̂𝑂 (𝑔)
2 2 4 2

∆𝐻̂𝑟2 (25℃) − ∆𝐻 ̂𝑟1 (25℃) = 2(𝐻 ̂𝐻 𝑂(𝑣) − 𝐻̂𝐻 𝑂(𝑙) ) = 2∆𝐻

̂𝑣 (25℃)𝐻 𝑂
2 2 2
o
The heat of vaporization of water at 25 C can be calculated by constructing a process path
between initial (liquid water at 25oC) and final (water vapor at 25oC) states. Verify that:
̂𝑣 (25℃)𝐻 𝑂 = 43.76 kJ/mol
∆𝐻 2
 For calculating the specific internal energy change corresponding to a given reaction:
̂=𝐻
𝑈 ̂ − 𝑃𝑉̂ ⇒ ∆𝑈 ̂ = ∆𝐻̂ − ∆(𝑃𝑉̂ )
̂𝑟 (𝑇, 𝑃) = ∆𝐻
∆𝑈 ̂𝑟 (𝑇, 𝑃) − ∆(𝑃𝑉̂ ) = ∆𝐻 ̂𝑟 (𝑇, 𝑃) − 𝑃∆𝑉̂ ; (since P=constant for ∆𝐻 ̂𝑟(𝑇,𝑃) )
Assuming ideal gas behavior for gaseous reactant and product species, and negligible specific
volume change for solid and liquid species, we can write 𝑃∆𝑉̂ terms for general reaction
∑𝜈𝑖 𝑆𝑖 ≡ 0 as:

𝑃∆𝑉̂ = 𝑅𝑇 ( ∑ |𝜈𝑖 | − ∑ |𝜈𝑖 |)

𝑔𝑎𝑠 𝑝𝑑𝑡 𝑔𝑎𝑠 𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡

̂𝑟 (𝑇, 𝑃) = ∆𝐻
⇒ ∆𝑈 ̂𝑟 (𝑇, 𝑃) − 𝑅𝑇 ( ∑ |𝜈𝑖 | − ∑ |𝜈𝑖 |)
𝑔𝑎𝑠 𝑝𝑑𝑡 𝑔𝑎𝑠 𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡
Hess's Law: If the stoichiometric equation for reaction (1) can be obtained by algebraic sum of
stoichiometric equation of reaction (2),(3), (4),......., then the heat of reaction can be obtained by
performing same algebraic operation on heat of reaction of reactions (1), (2), (3)....
𝑟𝑥𝑛1 = 𝑎2 𝑟𝑥𝑛2 + 𝑎3 𝑟𝑥𝑛3 + 𝑎4 𝑟𝑥𝑛4 + ⋯.
⇒ ∆𝐻̂𝑟1 = 𝑎2 ∆𝐻̂𝑟2 + 𝑎3 ∆𝐻 ̂𝑟3 + 𝑎4 ∆𝐻
̂𝑟4 + ⋯.
Formation reaction and heat of formation: A formation reaction is one in which 1 mole of a compound
is formed at 25oC and 1 atm from its element constituents as they occur in nature at 25oC and 1 atm. The
enthalpy change associated with formation reaction is known as heat of formation. For example, the
formation reaction for NH4NO3 is:
3
𝑁2 (𝑔) + 2𝐻2 (𝑔) + 𝑂2 (𝑔) → 𝑁𝐻4 𝑁𝑂3 (𝑠); ∆𝐻 ̂𝑟 (25℃, 1𝑎𝑡𝑚) = −365.14 kJ/mol
2
The elements that constitute NH4NO3 are N, H, and O and they occur in nature at 25oC and 1atm as N2(g),
O2(g), and H2(g). The heat of formation is:
̂𝑓 (25℃) or ∆𝐻
∆𝐻 ̂𝑓° = ∆𝐻̂𝑟 (25℃, 1𝑎𝑡𝑚) = −365.14 kJ/mol
By definition of formation reaction:
(∆𝐻̂𝑓° ) = (∆𝐻 ̂𝑓° ) = (∆𝐻 ̂𝑓° ) = 0; similarly for all other elemental species
𝑂2 𝑁2 𝐻2
Using Hess's law, the heat of reaction can be written in terms of heats of formation of the reactant and
product species as:
 ̂𝑓° ) −
̂𝑟° = ∑|𝜈𝑖 | (∆𝐻
∆𝐻 ̂𝑓° )
∑ |𝜈𝑖 | (∆𝐻
𝑖 𝑖
𝑝𝑑𝑡 𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡
Standard Heats of combustion ̂ °𝒄 : The
∆𝑯 enthalpy change associated with the complete combustion
with oxygen of a combustible species to yield specified products when both reactant and products species
of combustion reaction are at 25oC and 1 atm (or any other arbitrary reference T and P). The assumptions
for product species are: (i) all C will form CO2(g), (ii) all hydrogen will form H2O(l), (iii) all Sulfur forms
SO2(g), and (iv) all nitrogen forms N2(g). As an example, heat of combustion of liquid acetic acid is
871.69 kJ/mol which means:
𝐶𝐻3 𝐶𝑂𝑂𝐻 (𝑙) + 3𝑂2 (𝑔) → 2𝐶𝑂2 (𝑔) + 2𝐻2 𝑂(𝑙); ∆𝐻 ̂𝑟° = ∆𝐻 ̂𝑐° = −871.69 kJ/mol
The standard heats of reaction that involve only combustible reactant and product species can be
calculated from standard heats of combustion using Hess's law:
̂𝑟° =
∆𝐻 ̂𝑓° ) − ∑|𝜈𝑖 | (∆𝐻
∑ |𝜈𝑖 | (∆𝐻 ̂𝑓° )
𝑖 𝑖
𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡 𝑝𝑑𝑡
If any of the reactive species are themselves combustion products (CO2(g), H2O(l), SO2(g)....), their heats
of combustion in above equation should be set equal to zero.
Problem-1: The standard heat of combustion of liquid n-butane is 2855.6 kJ/mol. Calculate the standard
heat of reaction of the following reaction if the latent heat of vaporization of water is 44 kJ/mol and
butane is 19.2 kJ/mol at 25oC.
13
𝐶4 𝐻10 (𝑔) + 𝑂2 (𝑔) → 4𝐶𝑂2 (𝑔) + 5𝐻2 𝑂(𝑣); ∆𝐻 ̂𝑟1
°
=?
2
Solution:
13
𝐶4 𝐻10 (𝑙) + 𝑂2 (𝑔) → 4𝐶𝑂2 (𝑔) + 5𝐻2 𝑂(𝑙); ∆𝐻 ̂𝑟2
°
= −2855.6 kJ/mol
2
̂𝑣 )
(∆𝐻 = 44.0 kJ/mol; (∆𝐻 ̂𝑣 ) = 19.2 kJ/mol
𝐻 𝑂
2 𝐶 𝐻
4 10
13
̂𝑟1
∆𝐻 °
= 4𝐻̂𝐶𝑂 (𝑔) + 5𝐻 ̂𝐻 𝑂(𝑣) − 𝐻 ̂ −𝐻 ̂𝐶 𝐻 (𝑔)
2 2
2 𝑂2 (𝑔) 4 10

13
̂𝑟2
∆𝐻 °
= 4𝐻̂𝐶𝑂 (𝑔) + 5𝐻 ̂𝐻 𝑂(𝑙) − 𝐻 ̂ (𝑔) − 𝐻 ̂𝐶 𝐻 (𝑙)
2 2
2 𝑂2 4 10

̂𝑟1
∆𝐻 ° ̂𝑟2
− ∆𝐻 ° ̂ ̂ ̂ ̂
= 5(𝐻𝐻2 𝑂(𝑣) − 𝐻𝐻2 𝑂(𝑙) ) − (𝐻𝐶4 𝐻10 (𝑔) − 𝐻𝐶4 𝐻10 (𝑙) ) = 5(∆𝐻 ̂𝑣 ) ̂𝑣 )
− (∆𝐻
𝐻
2𝑂 𝐶
4 𝐻10
̂𝑟1
∆𝐻 ° ̂𝑟2
− ∆𝐻 °
= 5 × 44 − 19.2 = 200.8 kJ/mol
̂ °
∆𝐻𝑟1 = −2855.6 + 200.8 = −2654.8 kJ/mol
Problem-2: Calculate the amount of required heat transfer for the following reaction if it takes place in a
batch reactor (closed vessel) at constant volume and a constant temperature of 25oC.

Given: H f C2 H 4 ( g )
 52.283 kJ/mol,  H 
f CH 4 ( g )
 74.84 kJ/mol
C2H4 (g) + 2H2 (g)  2CH4 (g)

Solution

Closed system

⇒ 𝑄 = ∆𝑈𝑟 (250 C)

∆𝐻𝑟0 = 2 (∆𝐻𝑓0 ) − (∆𝐻𝑓0 ) − (∆𝐻𝑓0 ) = −201.963 kJ/mol

𝐶𝐻4 (𝑔) 𝐶2 𝐻4 𝐻2

̂𝑟0 − 𝑅𝑇(∆𝑛) = −199.485 kJ/mol

𝑄 = ∆𝑈𝑟 (250 C) = ∆𝐻
Problem-3: Calculate the standard heat of formation of CH4(g), given the following experimental results
at 25oC and 1 atm (Q is for complete reaction):

H2(g) + 1/2 O2(g) → H2O(l) Q = -285.84 kJ/mol

C(s) + O2(g) →CO2(g) Q = -393.51 kJ/mol
CH4(g) + 2O2(g) →CO2(g) + 2H2O(l) Q = -890.36 kJ/mol
A batch reactor is charged with 10 mol of H2(g) and 10 mol of C(s). Methane gas formation occurs in the
reactor while the temperature and pressure are maintained at 25oC and 1 atm. How much heat is released
after 5 moles of hydrogen is consumed?

Solution
𝐶(𝑠) + 2𝐻2 (𝑔) → 𝐶𝐻4 (𝑔) ̂𝑓0 =?
∆𝐻

Reaction 4 = (Reaction 2) + 2(Reaction 1) – (Reaction 3)

̂𝑓0 = 𝑄2 + 2𝑄1 − 𝑄3 = −74.83 kJ/mol

∆𝐻

Closed system

⇒ 𝑄 − 𝑊 = ∆𝑈 ⇒ 𝑄 = 𝑊 + ∆𝑈

̂𝑟 = ∆𝐻
∆𝑈 ̂𝑟 − 𝑅𝑇(∆𝑛) = −72.4 kJ/mol

−72.4 kJ
∆𝑈 = × 5 mol 𝐻2 consumed = −181 kJ
2 mol 𝐻2 consumed

𝐶(𝑠) + 2𝐻2 (𝑔) → 𝐶𝐻4 (𝑔)

t=0 10 mol 10 mol 0 mol

time=t 7.5 mol 5 mol 2.5 mol (gas moles)

Volume occupied due to gas moles,

𝑛𝑅𝑇
(𝑉𝑔𝑎𝑠 ) = 𝑉1 = = 0.2445 m3
𝑖𝑛𝑖𝑡𝑖𝑎𝑙 𝑃

(𝑉𝑔𝑎𝑠 ) = 𝑉2 = 0.183 m3
𝑓𝑖𝑛𝑎𝑙

𝑊 = 𝑃∆𝑉 = 𝑃(𝑉2 − 𝑉1 ) = −6.181 kJ

Hence,

𝑄 = 𝑊 + ∆𝑈 = 187.181 kJ
 Energy Balances on Mixing and reactive processes
Energy Balances methodology for reactive processes

The general procedure for solving energy balance problems which involve reaction is essentially same as
for non-reactive system with the only difference being in incorporating enthalpy changes due to reaction
in calculation of ∆𝐻̇ or ∆𝑈 term. The steps remain the same: (i) Draw a completely labeled flowchart, (ii)
Solve the material balances as much as possible, (iii) Identify the type of system (open or closed) and
accordingly write down the appropriate form of energy balance equation. Neglecting KE and PE and
assuming zero work transfer, the energy balance equation is (for open system):
𝑄̇ = ∆𝐻̇
The difference appears after this step i.e. in choosing the reference state and accordingly in expanding the
above equation to solve for unknown. Two methods are commonly used to choose the reference state: (i)
Heat of reaction method, and (ii) Heat of formation method. We discuss these two approaches by
considering the following combustion reaction occurring in a furnace.
13
𝐶4 𝐻10 (𝑔) + 𝑂2 (𝑔) → 4𝐶𝑂2 (𝑔) + 5𝐻2 𝑂(𝑣); ∆𝐻 ̂𝑟 (25℃) = −2834 kJ/mol
2

The flowchart and mass balances are already solved in the above diagram. The given system is open
system and hence energy balance will reduce to (assuming zero KE and PE changes):
𝑄̇ = ∆𝐻̇
Heat of reaction method: This is preferred method when a single reaction is involved in the process. The
reference state is taken as reactant and product species at 25oC and 1 atm (or a reference T and P at which
heat of reaction is known). The reference state for non-reactive species can be taken as any convenient T,
for example, inlet or outlet temperature or reference state used in thermodynamic table etc. Butane,
oxygen, carbon dioxide, and water are reactive species and hence the reference state accordingly is:
𝐶4 𝐻10 (𝑔), 𝑂2 (𝑔), 𝐶𝑂2 (𝑔), 𝐻2 𝑂(𝑣) @ 25℃
The reference state for nitrogen can be taken as: N2(g) @ 300oC if specific heat capacity is known or
N2(g) @ 25oC if thermodynamic table for nitrogen is available. Assuming that specific heat capacity is
known:
The rate of change of enthalpy is then given as:
∆𝐻̇ = 𝜁∆𝐻 ̂𝑟 (25℃) + ∑(𝑛𝑜𝑢𝑡 𝐻 ̂𝑜𝑢𝑡 ) − ∑(𝑛𝑖𝑛 𝐻̂𝑖𝑛 ); for single reaction

∆𝐻̇ = ∑ ̂𝑟𝑖 (25℃) + ∑(𝑛𝑜𝑢𝑡 𝐻

𝜁𝑖 ∆𝐻 ̂𝑜𝑢𝑡 ) − ∑(𝑛𝑖𝑛 𝐻
̂𝑖𝑛 ); for multiple reactions
𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛𝑠
The expansion of enthalpy change for above process will be:
∆𝐻̇ = 𝜁∆𝐻̂𝑟 (25℃)
̂𝐶𝑂
+ [360𝐻 ̂𝐻 𝑂(𝑣,1000℃) + 10𝐻
+ 450𝐻 ̂𝐶 𝐻 (𝑔,1000℃) + 150𝐻
̂𝑂 (𝑔,1000℃)
2(𝑔,1000℃) 2 4 10 2

̂𝑁 (𝑔,1000℃) ] − [100𝐻
+ 2765𝐻 ̂𝐶 𝐻 (𝑔,25℃) + 735𝐻
̂𝑂 (𝑔,300℃) + 2765𝐻
̂𝑁 (𝑔,300℃) ]
2 4 10 2 2
10 − 100
𝜁= = 90
−1
 ̂𝑁 (𝑔,300℃) = 0 due to choice of reference state
𝐻 2
Evaluating each specific enthalpy term one by one in above equation:
1000
̂𝐶𝑂
𝐻 =∫ (𝐶𝑝 )𝐶𝑂 𝑑𝑇 or using thermodynamic tables = 48.60 kJ/mol
2(𝑔,1000℃) 2
25
1000
̂𝐻 𝑂
𝐻 =∫ (𝐶𝑝 )𝐻 𝑑𝑇 or using thermodynamic tables = 37.69 kJ/mol
2 (𝑣,1000℃)
2 𝑂(𝑣)
25

1000
̂𝐶 𝐻 (𝑔,1000℃) = ∫
𝐻 (𝐶𝑝 )𝐶 𝑑𝑇
4 10
25 4 𝐻10 (𝑔)

1000
̂𝑂
𝐻 =∫ (𝐶𝑝 )𝑂 𝑑𝑇 or using thermodynamic tables = 32.47 kJ/mol
2 (𝑔,1000℃)
25 2 (𝑔)
1000
̂𝑁
𝐻 =∫ (𝐶𝑝 )𝑁 𝑑𝑇 or using thermodynamic tables = (30.56 − 8.12)kJ/mol
2 (𝑔)
2 (𝑔,1000℃)
300
300
̂𝐶 𝐻 (𝑔,300℃) = ∫
𝐻 (𝐶𝑝 )𝐶 𝑑𝑇
4 10
25 4 𝐻10 (𝑔)
300
̂𝑂
𝐻 =∫ (𝐶𝑝 )𝑂 𝑑𝑇 or using thermodynamic tables = 8.47 kJ/mol
2 (𝑔)
2 (𝑔,300℃)
25
Thus, substituting all the values in reduced energy balance equation, we obtain required heat transfer rate:
𝑄̇ = ∆𝐻̇
Note that the above method for calculating enthalpy change is equivalent to the hypothetical path shown
below:
∆𝐻1 ∆𝐻2 ∆𝐻3
𝑅𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠 @𝑇𝑖𝑛 → 𝑅𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠 @ 25℃ (𝑜𝑟 𝑇𝑟𝑒𝑓 ) → 𝑃𝑟𝑜𝑑𝑢𝑐𝑡𝑠 @25℃ → 𝑃𝑟𝑜𝑑𝑢𝑐𝑡𝑠 @𝑇𝑜𝑢𝑡
∆𝐻̇ = ∆𝐻1 + ∆𝐻2 + ∆𝐻3
̂𝑖𝑛 ; ∆𝐻3 = ∑ 𝑛𝑜𝑢𝑡 𝐻
∆𝐻1 = − ∑ 𝑛𝑖𝑛 𝐻 ̂𝑜𝑢𝑡 ; ∆𝐻2 = 𝜁∆𝐻
̂𝑟 (25℃)
𝑖𝑛 𝑜𝑢𝑡
Heat of formation method: This method is preferred for systems involving multiple reactions. However,
we will outline the approach using the combustion reaction process given in previous discussion.
The reference state are taken as elemental (or atomic) species which constitute the reactants and products
in the states in which elements are found at 25oC and 1 atm. The non-reactive species reference state is
again taken as per convenience. For above example, the reactive species are:
𝐶4 𝐻10 (𝑔), 𝑂2 (𝑔), 𝐶𝑂2 (𝑔), 𝐻2 𝑂(𝑣)
The elements that constitute these species are C, H, and O and they occur as C(s), O2(g), and H2(g) at
25oC and 1 atm. Thus, the reference state chosen is C(s), O2(g), and H2(g) at 25oC and 1 atm. For non-
reactive species (nitrogen), let us choose N2(g) at 25oC and 1 atm (this is the reference state in
thermodynamic tables for several gases) as the reference state.
The change in enthalpy is simply given as:
∆𝐻̇ = ∑ 𝑚̇𝑜𝑢𝑡 𝐻
̂𝑜𝑢𝑡 − ∑ 𝑚̇𝑖𝑛 𝐻
̂𝑖𝑛
𝑜𝑢𝑡 𝑖𝑛
For the given process:
∆𝐻̇ = [360𝐻 ̂𝐶𝑂
2(𝑔,1000℃)
̂𝐻 𝑂(𝑣,1000℃) + 10𝐻
+ 450𝐻 2
̂𝐶 𝐻 (𝑔,1000℃) + 150𝐻
4 10
̂𝑂 (𝑔,1000℃)
2

̂𝑁 (𝑔,1000℃) ] − [100𝐻
+ 2765𝐻 ̂𝐶 𝐻 (𝑔,25℃) + 735𝐻
̂𝑂 (𝑔,300℃) + 2765𝐻
̂𝑁 (𝑔,300℃) ]
2 4 10 2 2

The specific enthalpy for non-reactive species i.e. nitrogen is determined using thermodynamic tables:
𝐻̂𝑁 (𝑔,300℃) = 8.12 kJ/mol; 𝐻 ̂𝑁 (𝑔,1000℃) = 30.56 kJ/mol
2 2
For CO2(g, 1000oC), first form CO2(g) at 25oC from C(s,25oC) and O2(g,25oC) and then heat CO2 formed
to 1000oC. Thus,
̂𝐶𝑂 °
̂𝑓@25℃
𝐻 2(𝑔,1000℃)
= (∆𝐻 )
𝐶𝑂2
1000
+ (∫ (𝐶𝑝 )𝐶𝑂 𝑑𝑇 or using thermodynamic tables = 48.60 kJ/mol)
2
25

̂𝐶𝑂
𝐻 = −393.5 + 48.60 = −344.9 kJ/mol
2(𝑔,1000℃)
̂𝐻 𝑂(𝑣,1000℃) = (∆𝐻 °
̂𝑓@25℃
𝐻 2
)
𝐻2 𝑂(𝑣)
1000
+ (∫ (𝐶𝑝 )𝐻 𝑑𝑇 or using thermodynamic tables = 37.69 kJ/mol)
2 𝑂(𝑣)
25
̂𝐻 𝑂(𝑣,1000℃) = −241.83 + 37.69 = −204.1
𝐻 2

1000
̂𝐶 𝐻 (𝑔,1000℃) = (∆𝐻 °
̂𝑓@25℃
𝐻 ) +∫ (𝐶𝑝 )𝐶 𝑑𝑇
4 10 𝐶4 𝐻10 (𝑔) 4 𝐻10 (𝑔)
25
1000
̂𝐶 𝐻 (𝑔,1000℃) = −124.7 + ∫
𝐻 (𝐶𝑝 )𝐶 𝑑𝑇
4 𝐻10 (𝑔)
4 10
25
̂𝑂 (𝑔,1000℃) = (∆𝐻 °
̂𝑓@25℃
𝐻 2
)
𝑂2 (𝑔)
1000
+ (∫ (𝐶𝑝 )𝑂 𝑑𝑇 or using thermodynamic tables = 32.47 kJ/mol)
25 2 (𝑔)

̂𝑂 (𝑔,1000℃) = 0 + 32.47 kJ/mol

𝐻 2
̂𝑁
𝐻 −𝐻 ̂𝑁 = (30.56 − 8.12)kJ/mol
2 (𝑔,1000℃) 2 (𝑔,300℃)

̂𝐶 𝐻 (𝑔,25℃) = (∆𝐻 °
̂𝑓@25℃
𝐻 4 10
)
𝐶4 𝐻10 (𝑔)
̂𝑂 (𝑔,300℃) = 32.47 kJ/mol
𝐻 2

(𝐶𝑝 )𝐶 = 0.0923 + 27.88 × 10−5 𝑇 in kJ/mol ℃; 𝑇 𝑖𝑛 ℃

4 𝐻10 (𝑔)
Substitute all calculated values to get heat transfer rate.

The heats of combustion and heats of formation data for various substances are tabulated in
literature, for example, refer Table B.1 in Appendix B of Richard M. Felder, and Ronald W.
Rousseau, Elementary principles of chemical processes, 2009, 3rd edition, Wiley India
This data can be used to calculate heat of reaction of various reactions using Hess's law.
Problem-1: A jacketed vessel reactor is used to carry out oxidation of ammonia:
4𝑁𝐻3 (𝑔) + 5𝑂2 (𝑔) → 4𝑁𝑂(𝑔) + 6𝐻2 𝑂(𝑣); ∆𝐻 ̂𝑟° = −905 kJ/mol
Ammonia and oxygen are fed at a rate of 100 mol/s and 200 mol/s respectively, at 25oC into the jacketed
reactor vessel. The ammonia gets completely consumed in the reactor. Water is used as coolant and flows
at a rate of 60 kg/s in the jacket of the vessel. Water enters the jacket at 20 oC and leaves as saturated
liquid at 1 atm. Calculate the temperature of exit stream from the reactor assuming that the reaction vessel
combined with jacket is perfectly insulated. Given:
(𝐶𝑝 )𝑁𝑂(𝑔) = 0.0295 kJ/mol ℃; (𝐶𝑝 )𝐻 𝑂(𝑣) = 0.03346 kJ/mol ℃; (𝐶𝑝 )𝑂 (𝑔) = 0.0291 kJ/mol ℃
2 2
Solution

Since the jacketed reaction vessel is completely insulated, all the heat released due to occurring of
reaction is taken away by the cooling water.

The reaction process is shown below:

𝑄̇ = −𝑚̇𝑤𝑎𝑡𝑒𝑟 𝐶𝑝𝑤𝑎𝑡𝑒𝑟(𝑙) (𝑇 𝑠𝑎𝑡 − 20) = 60 × 4.184 × (100 − 20) = −20083.2 kJ/s

(Negative sign considering reaction vessel excluding jacket as system and thus, heat is transferred out of
the system)

The material balance problem has already been solved (straight-forward using stoichiometric equation).
We are given single reaction with known heat of reaction, thus, let us use heat of reaction method.

Reference states: NH3(g), O2(g), NO(g), H2O(v) all at 25oC and 1 atm.

𝑄̇ = ∆𝐻̇ = 𝜁∆𝐻
̂𝑟° + ∑(𝑛𝑜𝑢𝑡 𝐻
̂𝑜𝑢𝑡 ) − ∑(𝑛𝑖𝑛 𝐻
̂𝑖𝑛 )

0 − 100
𝜁= = 25; calculated based on ammonia
−4
̂𝑜𝑢𝑡 ) = 100𝐻
∑(𝑛𝑜𝑢𝑡 𝐻 ̂𝑁𝑂(𝑔,𝑇) + 150𝐻
̂𝐻 𝑂(𝑣,𝑇) + 75𝐻
̂𝑂 (𝑔,𝑇)
2 2

̂𝑖𝑛 ) = 100𝐻
∑(𝑛𝑖𝑛 𝐻 ̂𝑁𝐻 (𝑔,25℃) + 200 𝐻
̂𝑂 (𝑔,25℃)
3 2

̂𝑁𝐻 (𝑔,25℃) = 𝐻
𝐻 ̂𝑂 (𝑔,25℃) = 0 because of choice of reference state
3 2

𝑇
̂𝑁𝑂(𝑔,𝑇) = ∫ (𝐶𝑝 )
𝐻 𝑑𝑇 = 0.0295(𝑇 − 25)
𝑁𝑂(𝑔)
25

𝑇
̂𝐻 𝑂(𝑣,𝑇) = ∫ (𝐶𝑝 )
𝐻 𝑑𝑇 = 0.03346(𝑇 − 25)
2 𝐻 2 𝑂(𝑣)
25
 𝑇
̂𝑂 (𝑔,𝑇) = ∫ (𝐶𝑝 )
𝐻 𝑑𝑇 = 0.0291(𝑇 − 25)
2 (𝑔)
2 𝑂
25

̂𝑜𝑢𝑡 ) = 100𝐻
∑(𝑛𝑜𝑢𝑡 𝐻 ̂𝑁𝑂(𝑔,𝑇) + 150𝐻
̂𝐻 𝑂(𝑣,𝑇) + 75𝐻
̂𝑂 (𝑔,𝑇)
2 2

̂𝑜𝑢𝑡 ) = [100 × 0.0295 + 150 × 0.03346 + 75 × 0.0291](𝑇 − 25) = 10.1515(𝑇 − 25)

∑(𝑛𝑜𝑢𝑡 𝐻

𝑄̇ = 25(−905) + 10.1515(𝑇 − 25) − 0 = −20083.2

⇒ 𝑇 = 275.4℃
Problem-2: The production of ethanol from hydration of ethylene involves the following two reactions
(first is the desired reaction while second is undesired):
C2H4 (g) + H2O (v)  C2H5OH (v)
2 C2H5OH (v)  (C2H5)2O (v) + H2O (v)

The feed to a continuous reactor for producing ethanol from ethylene contains 53.7 mole% C2H4, 36.7%
H2O, and the balance N2 which enters the reactor at 310oC. The reactor operates isothermally at 310oC.
An ethylene conversion of 5% is achieved, and the yield of methanol (moles ethanol produced/mole
ethylene consumed) is 0.90.
a. Assuming 1 mol/min of feed to the reactor as basis, calculate the molar amount of each species
in reactor output stream (Degree of freedom analysis is not required).
b. Calculate the reactor heating or cooling requirement in kJ/min. Also, write down the
assumptions involved, if any. Use heat of formation method.
Solution

(a) 5% 𝐶2 𝐻4 conversion ⇒ 𝑛1 = 0.95 × 0.537 = 0.510 mol 𝐶2 𝐻4

⇒ consumed = 0.02685 mol 𝐶2 𝐻4

yield = 0.9 ⇒ 𝑛3 = 0.024165 mol 𝐶2 𝐻5 𝑂𝐻

C balance: 2 × 0.537 = 2𝑛1 + 2𝑛3 + 4𝑛4 ⇒ 𝑛4 = 1.4175 × 10−3 mol 𝐷𝐸

H balance: 4× 0.537 + 2 × 0.367 = 4𝑛1 + 2𝑛2 + 6𝑛3 + 10𝑛4 ⇒ 𝑛2 = 0.3414 mol 𝐻2 𝑂

Or apply overall balance: 𝑄 − 𝑊 = ∆𝐻 + ∆𝐾𝐸 + ∆𝑃𝐸

(b) Assumptions: 𝑊, ∆𝐾𝐸, ∆𝑃𝐸 = 0 ⇒ 𝑄 = ∆𝐻

̂𝑜𝑢𝑡 − ∑ 𝑛𝑖𝑛 𝐻
𝑄 = ∑ 𝑛𝑜𝑢𝑡 𝐻 ̂𝑖𝑛

̂𝐶 𝐻 (𝑔,3100 C) + 𝑛2 𝐻
= [𝑛1 𝐻 ̂𝐻 𝑂(𝑣,3100 C) + 𝑛3 𝐻
̂𝐶 𝐻 𝑂𝐻(𝑣,3100 C) + 𝑛4 𝐻
̂𝐷𝐸(𝑣,3100 C) ]
2 4 2 2 5

̂𝐶 𝐻 (𝑔,3100 C) + 0.367 𝐻
− [0.537 𝐻 ̂𝐻 𝑂(𝑔,3100 C) ]
2 4 2

Reference state: 𝐶(𝑠), 𝐻2 (𝑔), 𝑂2 (𝑔) at 250 C

3100 C
̂𝐶 𝐻 (𝑔,3100 C) = (∆𝐻𝑓0 )
𝐻 + ∫250 C 𝐶𝑝 𝑑𝑇 = 68.68 kJ/mol
2 4 𝐶2 𝐻4 (𝑔,250 C)

3100 C
̂𝐶 𝐻 𝑂𝐻(𝑣,3100 C) = (∆𝐻𝑓0 )
𝐻 + ∫250 C 𝐶𝑝 𝑑𝑇 = −210.32 kJ/mol
2 5 𝐶2 𝐻5 𝑂𝐻
̂𝐻 𝑂(𝑣,3100 C) = (∆𝐻𝑓0 )
𝐻 ̂𝐻 𝑂(𝑣,3100 C) 𝑤.𝑟.𝑡.250 C = −232.3 kJ/mol
+𝐻
2 𝐻2 𝑂(𝑣) 2

3100 C
̂𝐷𝐸(𝑣,3100 C) = (∆𝐻𝑓0 )
𝐻 + ∫250 C 𝐶𝑝 𝑑𝑇 + ∆𝐻𝑣 (250 C) = −227.221 kJ/mol
𝐷𝐸

Hence, 𝑄 = −1.312 kJ