Physical Process Chemistry

CPI3011

Dr Shawn Gouws

Programme coordinator
Specific/learning outcomes
Upon completing this Unit, you should be able to:
• understand the definitions and physical meanings of dimensions
and units
• perform operations (i.e. addition, subtraction, multiplication, and
division) of numbers accompanied by corresponding units
• identify units commonly used in engineering and scientific
calculations
• convert one set of units (or one unit) associated with numbers
(or a number) or in an equation into another equivalent set of
units (or another unit), using a given conversion factor
• explain and use the concept of dimensional homogeneity
(consistency) of equations to identify units of specific numbers in
those equations
Specific/learning outcomes
 Upon completion of this module learners will be able to:
• Know and apply the terms, definitions and variables of
thermodynamics and reaction kinetics to selected processing
operations;
• Use the first and second law of thermodynamics to calculate key
properties of chemical process operations;
• Discuss and explain the structure of the inorganic chemical sector;
• Discuss and explain the various unit operations used in the processing
of inorganic raw materials.
Introduction
 Process chemistry is based upon the principles of quantitative science
• XYZ barrels of oil
• X cubic meters of air
• Z tons of X per hour
• Etc.
 As chemical technologist you need to be conversant with the use of
units accompanying certain quantities, and you need to be able to
perform calculations involving units speedily and correctly.
Definitions:
Physical quantities can be divided into one of two types, namely:
 Fundamental quantities
 Derived quantities
Definitions:
 Fundamental Quantities:
 A fundamental quantity cannot be expressed in simpler units. All other
quantities are derived from the fundamental quantities, and are referred
to as Derived Quantities.

There are SEVEN fundamental quantities:

 Length
 Mass
 Time
 Temperature
 Charge (current)
 Amount
 Luminous intensity
Definitions:
 Derived Quantities:
 Derived quantities are obtained from the multiplication or division of the
seven fundamental quantities.

Examples of derived quantities are:

 Area (length x length)
 Volume (length x length x length)
 Density (mass/volume or mass/(length x length x length)
 Velocity (length/time)

 List at least five additional derived quantities that you have already
learned
Definitions:
 Dimensions and Units:

 A dimension is a property that can be measured directly (e.g., length, mass,

temperature) or calculated, by multiplying or dividing with other dimensions
(e.g., volume, velocity, force).

 A unit is a selected reference quantity in terms of which all quantities of the

same kind can be expressed. Every physical quantity can be expressed as a
product of a pure number and a unit.

 Unit system: A specific system of expressing measurements of quantity, e.g. 1

meter, 1 yard, 1 furlong, etc.
Definitions:
Unit System
Physical Quantity
SI AE CGS*

Temperature Kelvin (K) Farenheit (oF) Celcius (oC)

Length Meter (m) Foot (ft) Centimeter (cm)

Mass Kilogram (kg) Pound (lb) Gram (g)

Time Second (s) Second (s) Second (s)

Charge Coulomb (C) Coulomb (C) Coulomb (C)

Amount mol - -
Luminous
can** - -
intensity
Definitions: Summary
 The “dimension” is the property that can be measured experimentally or
calculated
 To express the physical quantity of a dimension, we use a pure number and its
corresponding unit. (1 foot (1 ft), or 12 inches (12 in), or 30.45 centimeters
(30.45 cm).)
 A physical property such as length may therefore be expressed by a different
numerical value if it is accompanied with a different unit.
 The units of derived quantities (such as area) may also be expressed in different
units, hence by different numerical values.
 As a chemical technologist, you should be able to convert the numerical
values of fundamental and derived quantities from one unit system to
another, as well as derive the units for a derived quantity.
 Example: If the density of a liquid is defined as its volume divided by its mass,
what are the units for the density of a liquid in SI, AE, and CGS unit systems?
Calculations with units: Rules
Rule1: Only units that are in the same dimension can be added or subtracted.

Rule 2: Before the numerical values in the same dimension can be added or
subtracted, the units of those numerical values must be the same.

Rule 3: Any unit can be multiplied by, or divided by another unit. In the latter
case, units only cancel if they are the same.

Rule 4: In order to equate any terms (e.g. pV = nRT) in an equation, the terms on
both sides of the equal sign must be in the same dimension and unit. (This rule is
often referred to as the rule of “Dimensional consistency” and is extremely
useful in checking the correctness of one’s own calculations.)
Calculations with units: Examples
  
Calculations with units
Dimensional analysis, sometimes also called
factor-label method or unit analysis is a very
powerful technique in solving problems involving
units.
It allows you to set up the problem and check for
errors of logic before doing any actual calculations.
It also allows you to determine intermediate
answers of intermediate steps as you solve the
overall problem.
Calculations with units
Step 1: Define the Unknown: Clearly specify the units (dimensions) of the
answer (the unknown) to the problem. These units are the target units for your
equation.
Step 2: List all the Known quantities: List all the known quantities together
with their units.
Step 3: Conversion factors and formulas: List all the formulas and all
conversion factors (with their units) that you will require to make different units
consistent.
Step 4: Equation: Write down the equation (using appropriate formulas and
conversion factors) such that the units of the left side (the side containing the
known values) are equivalent to the units of the right side (the side containing the
unknown). If the units are not equal, then the problem has not been set up
correctly and further changes in the setup must be made.
Step 5: Calculate: Do the calculation only after you have completed step 4
above successfully.
Calculations with units
 Worked Example:
 Artificial hearts are often used in patients who are awaiting a donor heart. The
expected lifetime for such an artificial heart in a specific patient (as it will
differ from patient to patient) need to be estimated to ensure sufficient time
before a follow-up operation should be done. If an artificial heart pumps a
minimum of 17,000,000 pints of blood before failure, how long is it likely to
last in a patient whose average heart rate is 72 beats per minute, and the
average stroke volume (the amount of blood pumped with each stroke) of the
artificial heart is 70 mL?
Calculations with units
 Step 1: Define the Unknown (target units)
 We want to determine the number of years the heart can be expected to beat.
  
 Step 2: List all the Knowns
 The artificial heart is projected to pump at least 1.7 x 107 pints of blood
 The average heart rate is 72 strokes/minute
 The average stroke volume is 70 mL/stroke
  
 Step 3: Conversion factors and formulas
 There are 473 mL/pint
 There are 60 min/hr
 There are 24 hr/day
 There are 365 day/yr
Calculations with units
  
 Calculations with units
 
Calculations with units
 A man is painting a fence 300 meters long and 2.0 meters high with paint that
costs $23.00/ gallon. If a gallon of paint covers 60 square meters, what does it
cost to paint the fence in South African Rands when the exchange rate is $1 =
R11.21?
  Rachel has a rope of length 40 m. She gave 12 m 53 cm to Sam, 18 m 35 cm to
Ron and 9 m 7 cm to Jack. What length of rope is still left with Rachel?
Examples
 A sample of oil has a density of 0.85 g/mL. What is the mass of 3.00 barrels of
oil in kilograms if a barrel of oil is 42.0 gallons? 1 gallon = 3.8754L.

 The diameter and height of a vertical cylindrical tank are 5 ft and 6.5 ft
respectively. It is full up to 75% height with carbon tetrachloride (CCl4), the
density of which is 1.6 kg/ l. Find the mass in kilogram.

 Convert 23.16 lb.ft/min2 to kg.cm/ s2.

 Convert 120 hp to kJ/ min.
Prove the following:
 (i) 1 g/ cm3 = 62.42 lb/ ft3
 (ii) 1 Btu/( lb)( oF) = 1 kcal/( kg)( oC)
Introduction to SI units
  SI other units
Distance m dm cm mm
Area m2 dm2 cm2 mm2
Volume m3 dm3=1L cm3 = mL
Mass kg g
Density = mass / volumekg / m3 g / cm3
Force N
Pressure Pa = 1 N / m2 1 atm = 101.3 kPa
Energy = heat = work J ( Joule ) 1 kJ = 1000 J
Power 1 Watt = W = 1 J s-1
Molar energy J mol-1 kJ mol-1
 Some definitions W = force x distance ( Nm-1 )
Atmospheric pressure = 101300 Pa = 101.3 Pa
R = gas constant = 8.314 J mol-1 K-1
 In the physical chemistry context, everything around us is divided into two
parts, the system and its surroundings. The system is that part which we are
studying, and can be a beaker containing a reaction mixture, a reactor, an
engine, an electrochemical cell, and so on.
 open system, if matter can be transferred through the boundary between the
system and its surroundings ;
 a closed system, if matter can not pass through the boundary; in both these
systems energy can be transferred across the boundary, ie a closed system could
expand and push a piston against the surroundings;
 an adiabatic system is a closed system that does not allow any thermal energy
( heat ) to pass through its boundary; an
 an isolated system is a closed system which allows neither matter nor energy
to be transferred across its boundary. Fig 1 below illustrates these systems.
Types of systems

Surroundings surroundings surroundings T2 T1

system Matter
E
E M
E

E E
matter

Open closed isolated adiabatic

(T2≠T1)
 Work is done when an object is moved against an opposing force. It is
equivalent to a change in the height of a weight hanging somewhere in the
surroundings. An example of doing work is the expansion of a gas that pushes
out a piston and therefore raises a weight. A chemical reaction that produces a
gas also does work, since the atmosphere is pushed aside by the evolving gas.

Energy of a system is its capacity to do work. When work is done on an
isolated system, for ex by compressing a gas or winding a spring, its capacity to
do work is increased, so the energy of the system is increased. When the
system does work on the surroundings, for ex when the piston moves out or the
spring unwinds, its energy is reduced because it can do less work than before.
 Experiments have shown that the energy of a system, ie its capacity to do work,
may be changed by other means besides work. When the energy of a system
changes as a result of a temperature difference between it and the surroundings,
we say that energy has been transferred as heat. When we heat up a beaker of
water, the hot water will have more energy than the original cold water.
  
 A process that releases energy as heat is called exothermic. All combustion
reactions are exothermic. Processes which absorb energy as heat are called
endothermic. An example here is the vaporisation of water. An exothermic
process taking place in an adiabatic system results in a temperature rise, whilst
an endothermic process in a similar system will result in a decrease in
temperature.
 The first law of thermoynamics
In thermodynamics, the total energy of a system is called its internal energy U. This
internal energy is the total kinetic and potential energy of all the molecules present in
the system. The change in internal energy is indicated by ΔU and represents a
change of a system from an initial state, where the internal energy is U1 to a final state
of internal energy U2 :
U  U 2  U 1
The internal energy U is a state function since its value depends only on the current
state of the system and is independent of how that state has been reached..
Internal energy, heat and work are all measured in the same units, the Joule ( J ).
Changes in molar energy are expressed in kilojoules per mole ( kJ mol-1 ).
 
The internal energy of a system may be changed either by doing work on the
system or by heating it. Heat and work are equivalent ways of changing a system’s
internal energy. If a system is isolated from its surroundings, then no change in
internal energy can take place.
 
If we write w for the work done on a system, q for the energy transferred as heat to the
system and ΔU as the resulting change in internal energy of the system, then it follows
that :

U  q  w (2)

Equation 2 is the mathematical statement of the 1st law of thermodynamics, since it

summarises the equivalency of heat and work, and the fact that the internal energy of
an isolated system is constant ( here q = 0 and w = 0 ). A change in internal energy of
a system is equal to the energy in the form of heat or work that passes through its
boundary. There are variations of the 1st law :

a) The energy of an isolated system is constant : for an isolated system q = 0,

and w = 0, hence the total energy of an isolated system is constant : ΔU = Q +
w=0
b) An alternative equivalent expression is that energy in an open system may
be exchanged with the surroundings as either work or heat but may not be lost
or gained in any other way.
Problems :

1. An electric motor produces 15 kJ per second as mechanical work and looses 2

kJ per second as heat to the surroundings. Calculate the change in internal energy
of the motor. ( Answer = - 17 kJ per second )
2. When a spring is wound, 100 J of work was done on it, but 15 J escaped as
heat to the surroundings. Determine the change in internal energy. ( Answer = +
85 J )
Expansion work
 Here we will study the work arising from a change in volume. When a gas
expands it drives back the atmosphere and does work. Many chemical reactions
generate gas or adsorb gas.
 The calculation of expansion work starts with the definition of work : the work
required to move an object by a very small distance dz against an opposing
force of magnitude F is given by :
 dw = - F dz (4)
 The negative sign tells us that, when the system moves an object against an
opposing force, the internal energy of the system doing the work will decrease.
Now consider Fig 2, where a piston of area A can move against an external
pressure pex. Since pressure = force per unit area, the force on the outer face of
the piston is F = pex A. When the piston expands through a distance dz against
an external pressure pex, it follows that the work done by the system is : dw = -
pex A dz. But now A dz = the change in volume dV. Therefore the work done
by the system is :
 dw = - pex dV (5)

To obtain the total work when the volume changes from Vi to Vf, we need to
integrate eq 5 between the initial and final states :
Lets consider the reaction of propane ( C3H8) with O2 :
  C3H8 (g) + 5 O2 (g)  3 CO2 (g) + 4 H2O (g)
  6 moles of gas 7 moles of gas

If this reaction takes place in a container fitted with a movable piston, the piston
will move outward against the pressure of the atmosphere, thereby doing work. If
the atmospheric pressure, pex, is constant, the work done can be calculated from
the formula : w = - P ΔV. We note that since ΔV = positive, w will be negative.
 When a reaction takes place leading to a contraction of the volume, such as for
example :
3 H2 (g) + N2 (g)  2 NH3 (g)
 the work w will be positive, since ΔV now will be negative.
 Off course if there is no volume change, then the work w = 0.
Types of expansions
1. Free expansion
By free expansion we mean expansion against zero opposing force, when pex = 0.
From eq 5, since dw = 0, we have w = 0. No work is done when the system
expands freely. This type of situation arises when a system expands in a vacuum.
2. Expansion against pressure

3. Reversible expansion
A reversible expansion in thermodynamics is a change that can be reversed by an
infinitesimal change in a variable. The word reversible means something that can
change direction
If the pressure of the external gas is reduced slightly, the piston will expand very
slighly, increasing the volume of the confined gas; if the external pressure is increased
very slightly , the volume of the confined gas will decrease very slightly.

In eq 6 we can now put pex = p :

Vf

w    pdV (8)
Vi

The integral can be evaluated once we now the relation between p and V
 Isothermal reversible expansion

Consider the reversible isothermal expansion of a perfect gas ( temperature

constant, for ex using a constant temperature bath ). Since the ideal gas equation
is pV = nRT, we know that at any stage p = nRT / V, with V the volume of the gas
at that stage. Since the temperature T is constant and n and R are also constants,
all these can be taken outside the integral, so that for a reversible isothermal
expansion of an ideal gas
Excersices
Problem 1
Calculate the work done when 40 g of iron reacts with HCl in
a) a closed beaker of fixed volume
b) an open beaker at 25 0C. ( A = - 1.78 kJ )

Problem 2
Calculate the expansion work done when 100 g of water is electrolysed under constant pressure at 25
0C. ( A = - 20 kJ )

Problem 3
A sample of Argon ( Ar, atomic mass 39.95 g / mol ) of mass 6.56 g occupies 18.5 L at 305 K.
a) calculate the work done when the gas expands isothermally against a constant external pressure of
7.7 kPa until its volume has increased by 2.5 L ( A = - 19.25 J )
b) calculate the work that would be done if the same expansion occurred reversibly.
( A = –52.71 J )
Enthalpy
We shall now learn that the heat supplied at constant pressure during expansion
work is equal to the change of an important thermodynamic property called
enthalpy, H, defined as :
 
H = U + pV (10)
 
Here p is the pressure of the system and V its volume. Because U, p and V are all
state functions, H is also a state function. A state function is one whose value
depends only on the present state or condition of the system and not on the path
used to arrive at that condition. Pressure, volume and temperature are other state
functions. This means that for a change ΔH from one initial state to a final state,
the value ΔH is independent of the path between them.
The change in enthalpy is equal to the heat supplied at constant pressure to a
system, when this system does not do any additional work :
 
dH = dqp ( constant p, no additional work ) (11)
 
For a measurable change :
 
ΔH = qp (12)
 An enthalpy change is measured calorimetrically by monitoring the temperature
change that accompanies a physical or chemical change taking place at constant
pressure. A common instrument used for this is the bomb calorimeter which will
be discussed later.
a) Relating ΔH and ΔU
 
The enthalpy of a perfect gas is related to its internal energy by pV = nRT:
 H = U + pV = U + n RT (13)
 
This equation implies a change in enthalpy in a reaction that produces or
consumes gas is :
 ΔH = ΔU + ΔngRT (14)
 
In eq 14, Δng is the change in the number of moles of gas in the reaction; for ex
 2 H2 (g) + O2 (g) —> 2 H2O (l) Δng = - 3 mol
 The change in number of moles of gas is -3 since we have 3 moles of gas on the
reactant side of the equation but none on the product side. The difference ΔH -
ΔU =
( -3 ) x RT = - 7500 J = - 7.5 kJ.
Be careful with the units !
 b) Variation of enthalpy with temperature
  
 The enthalpy of a substance increases as its temperature is increased. The
relation between the increase in enthalpy and the increase in temperature
depends on whether the reaction is carried out at constant pressure or constant
volume. Usually constant pressure is more important ( since reactions are
normally carried out at atmospheric pressure ); in this case an important
quantity is the heat capacity at constant pressure, Cp, which is defined as the
slope of the graph of enthalpy versus temperature :
 Cp = ( δH / δT )p (15)
  
 The molar heat capacity at constant pressure Cpm is the heat capacity per mole
of substance.
  
 From eq 15 we find for infinitesimal changes in temperature:
 dH = Cp dT ( constant p ) (16)

 If the heat capacity of a substance is constant over a particular range of

temperatures, then for a measurable temperature increase :

 ΔH = Cp ΔT ( constant p ) (17)

 Now we remember that the heat transferred at constant pressure, qp is defined

as the enthalpy change ΔH, eq 17 can also be written as :


 qp = Cp ΔT (18)

 Using eq 18 one can measure the heat capacity of a substance simply by

supplying a measured quantity of heat under constant pressure conditions ( ie at
atmospheric pressure ) and measuring the resulting increase in temperature.
The variation of Cp with T can sometimes be ignored if the temperature range is
small or if the Cp value does not vary much over the temperature range selected.
If the Cp value varies with temperature, the following empirical expression is
used for Cp :

(19) c
C pm  a  bT  2
T
The values a, b and c are constants for each substance and are independent of
temperature. For ex for N2, a = 28.58, b = 3.77 x 10-3 , and c = - 0.50 x 10-5.
The values of a, b and c vary, therefore the molar heat capacity of N 2 will vary
with temperature
Example
 A steel pipe having a diameter of 0.742” and wall thickness of 0.154” is
subjected to inside and outside surface temperature of 200o and 160oF,
respectively. (k = thermal conductivity = 24.8Btu/hr oF) Find the heat flow rate
per foot of pipe length, and also the heat flux based on the inside and that based
on the outside surface area.

 qr = -kA dT/dr r0

 Heat flux ratio % =

ri
Ti
(qri – qro)/ qro
To
Example : Calculate the change in molar enthalpy ( ie the enthalpy of 1 mole )
of N2, when it is heated from 25 0C to 100 OC. Use heat capacity data given as
30 J mol-1
Problems
1. The value of Cpm for a sample of a perfect gas was found to vary with
temperature according to the expression : Cpm = 20.17 + 0.3665 T. Calculate qp,
w, ΔU and ΔH for one mole of gas, when the temperature is raised from 25 0C to
200 0C at
a) constant pressure ( Answer : qp=28.2 kJ, ΔH = 28.2 kJ, ΔU=26.766 kJ,
w=-1.434 kJ )
b) at constant volume ( Answer : qV=26.764 kJ, ΔU=26.764 kJ, w = 0,
ΔH=28.2 kJ )
 
2. When 3.0 mol O2 is heated at a constant pressure of 3.25 atm, its temperature
increased from 260 K to 285 K. Given that the molar heat capacity of O 2 at
constant pressure is 29.4 JK-1mol-1, calculate q, ΔH and ΔU
( answer q=+ 2.2 kJ, ΔH=+ 2.2 kJ, ΔU=+ 1.6 kJ )
 
Energy balance
 Heat balances are used to account for all of the energy that enters and leaves a
system. For any substance passing through a process, the change in enthalpy
represents the total amount of heat energy that has been used or generated by
the process. The second law of thermodynamics tells us that:

 Enthalpy Input  Enthalpy Output = Total Change in Heat Energy Occurring

in the System

The enthalpy change in a system is related to one or all of the following:

 Changes in physical state of the materials in the system
 Energy changes due to chemical reactions (endothermic or exothermic)
 Energy changes due to mechanical work performed on or by the system
State of matter
Principles of heat transfer
The amount of heat energy present in a substance determines the speed and
inertia of the molecules. The effects are typically seen in one of two forms:

 As a change in temperature (i.e., sensible heat)

 As a change in physical state (i.e., latent heat)

 
The changes occur because heat energy directly affects molecular motion by
exciting molecules and increasing their velocity This has two effects:

 The increase in molecular motion increases the number of collisions between

molecules, causing an increase in temperature.

 The increase in movement of the molecules causes the physical state of the
substance to change.
 
Sensible heat
Sensible heat, which can be detected by touch, refers to the heat energy used to
change the temperature of a substance and can be measured by that change in
temperature.
Temperature is:
 The heat energy stored in a substance as molecular motion.
 A quan­ti­ta­tive measure of the relative tendency of heat to escape from a
substance. The higher the temperature, the greater the ten­dency for heat energy
to escape.

Sensible heat is defined as a change in temperature only. It is the process of

either adding or removing temperature from a substance. A change in sensible
heat does not change the state of the material but is apparent as a change in
temperature
Latent heat
 Latent heat refers to the heat energy required to change the state of a substance.
During a change of state, the material does not change temperature. The
freezing point of a liquid is the temperature at which a change of state from
liquid to solid occurs. At the freezing point, the mole­cules within a liquid
rearrange from a ran­dom tumble to form a lattice structure. This change of
molecular arrangement requires heat energy to be given up, but there is no
change in temperature. Since the molecules are closer together, freezing causes
liquids to take up less space. The liquid becomes denser as it freezes.
 The latent heat required to vaporize 1 lb of water at its boiling point is 970 Btu.
 The latent heat of fusion is the amount of heat energy required to completely
melt a given amount of a solid, such as ice. Add­ing heat to the solid will not
increase its temperature until the entire solid has melted. The amount of heat
required to melt a substance is directly related to the quantity of the sub­stance.

 The latent heat required to melt 1 lb of ice into water at 32ºF is 18 Btu.
 The energy associated with latent heat is used throughout
chemical plant and refinery processes. This energy gives steam its
large heating capacity, as well as its ability to power turbines and
steam engines
 Heat transfer refers to the transfer of heat energy between substances at
different temperatures. The driving force behind heat transfer is the desire for
objects to be at thermal equilibrium, which is the state in which an object is at
the same temperature as its environment

 Radiation is the process of transmitting heat by electromagnetic waves.

Radiant heat energy transmits heat into a substance by exciting its molecules to
a higher speed and therefore a higher energy level. The higher the temperature
of a substance, the more radiant energy released.
Convection is the transfer of heat through the flow and mixing of a fluid(s). It
occurs when:
 Fluids flowing past a solid surface transfer heat to that surface.
 Heat from a solid surface is transferred to a fluid flowing in contact with it.
 The hot fluid gives up some of its energy to the colder fluid as a hot fluid
passes through a cold fluid. As long as heat is supplied, the fluid will continue
to circulate
Conduction is the simplest method of heat transfer and refers to the transfer of
heat through a solid. It occurs when heat is transferred from the outside surface
to the inside surface of a solid.

Conduc­tive heat transfer is driven by a temperature difference across the solid

being heated. The greater the temperature difference across the solid, the
greater the driving force and the more heat that is transferred
Summary
The first law of thermodynamics for a closed system is
U + Ek + Ep = Q−W
The first law of thermodynamics for an open system at steady state (i.e.,
continuous)
is
H + Ek + Ep = Q −W s
Procedure for energy balance calculations:
1. Draw and completely label a process flowchart.
2. Perform all material balance calculations.
3. Write the appropriate form of the energy balance equation and
remove any negligible terms.
4. Choose a reference state (phase-gas/liquid, T, P) for each species
involved. If using enthalpy tables, use reference state to generate
table. If no tables are available, choose one inlet or outlet condition
as the reference state for the species.
5. Construct an inlet–outlet enthalpy table.
6. Calculate all required values of ui or hi and insert the values into the
table.
7. Calculate ΔU or ΔH (e.g., ΔH = Σmihi − Σmihi).
8. Calculate any other terms in the energy balance equation (i.e., W,
ΔEk, ΔEp).
9. Solve for the unknown quantity in the energy balance equation.
1.Liquid methanol at 25°C is heated and vaporized for use in a chemical
reaction. How much heat is required to heat and vaporize 10 mol/s of
methanol to 600°C. (744 kJ/s)

Cp liq = 75.86 + 0.1683T

Cp vap = 42.53 + 0.083T
Bp = 64.7C
Hvap = 35.2 kJ / mol
Example
 Saturated steam at 0.276MPa flows inside a steel pipe having an inside
diameter of 2.09 cm and outside diameter of 2.67cm. The convective
coefficients on the inner and outer pipe surfaces may be taken as 5680 W/m 2. K
and 22.7W/m2K, respectively. The surrounding air is at 294K, find the heat loss
per meter pf bare pipe and for a pipe having a 3.8 cm thickness of 85%
magnesia insulation on its outer surface.

 R1 = Rconvection inside = 1/hiAi

 R2 = Rconvection outside = 1 /hoAo
 R3 = Rconduction = ln(ro/ri)/2π kL

 B) the inside temperature is that of 1915 Pa saturated steam, 267F or 404K.

Calculated the heat transfer per meter of pipe.
Example heat transfer
 Light lubricating oil (Cp = 2090 J/kgK) is cooled by allowing it to exchange
energy with water in a small heat exchanger. The oil enters and leaves the heat
exchanger at 375K and 350K, respectively, and flows at a rate of 0.5 kg/s.
Water at 280K is available in sufficient quantity to allow 0.201 kg/s to be used
for cooling purposes. Determine the required heat transfer for a) counterflow
and b) parallel flow operation. Overall heat transfer coefficient U = 250
W/m2K.

 Comment on which arrangement will have a lower area.

Introduction: Material balancing
 In this lesson, you learned about the differences between steady state and
unsteady state processes. Both material and energy balances can be useful
tools for monitoring the conditions of a process.
 In order to effectively monitor the changes taking place in a process, you must
be able to account for both the changes of state that may take place along with
the different types of heat transfer that may be occurring.
 This information will give you a more complete picture of what is happening in
your process and allow you to make the necessary adjustments to maximize
process efficiency
Principles of process, material and
energy balances
At the completion of this module, you will be able to:
 
1. Describe the principles of process balancing.
 
2. Describe the principles of material balancing.
 
3. Describe the principles of energy balancing.
Recap
A process is a collection of equipment that takes in materials and energy and
converts them into products. Processes usually produce:
 The desired products that are targeted by a series of reactions and/or physical
processes.
 Byproducts that come in with the feedstock or are created through side
reactions and have market value.
 Waste products that come in with the feedstock or are created through
unwanted reactions and have little or no market value. These products often
have a costly disposal.
Material Balance
In order to more effectively monitor process conditions to maintain steady state
and troubleshoot process upsets, it is necessary for the operator to know what
materials are coming into and leaving the process. One of the best tools for
monitoring material flow is a material balance. By performing a material
balance using information provided by process indicators and laboratory
analysis, the operator can account for all of the material in a given system to
identify system leaks or misdirected flow. Additionally, using the process
indicators and the results of a material balance, operators can:

 Adjust the process variables to maximize the desired product yield.

 Minimize losses within the system.

Introduction
 A material balance does not have to be done at the system level. There are
times when useful information can be obtained by tracking a single element or
component through the system. Additionally, a material balance at the system
or subsystem level helps to determine whether the unit is producing as
expected, material is building up in the process, there is unaccounted for
material leaving the process, or there is an instrumentation malfunction.
 An overall balance allows you to account for all of the material that goes into
and comes out of the process. A component balance follows one component,
like propane for instance, all the way through the process, and an elemental
balance accounts for just one element. Component balances and elemental
balances are very useful in determining the source of the unbalance
Importance of material balances
Process performance, efficiency and economics
• Monitor ratio of product output to raw material input
• Data required to evaluate economic gain/loss for production
processes/plants
Designing/sizing downstream equipment
• With known flow rates/batch sizes one can calculate size of
downstream equipment accurately
Energy balancing/optimisation
• Over/under-supply of heat cooling
Health and Safety
• Many applications, e.g. calculation of chemical energy inside
equipment vs design specifications of equipment
Conversion of matter
 Physical Changes in Materials
 Examples of physical changes that occur to materials as they are processed
include:
 Complex liquid mixtures are distilled and separated into individual
components.
 Feedstocks are blended into mixtures.
 Large solid pieces are ground to powder.
 Slurries and immiscible liquids are separated by settling.
 Dissolved solids are converted to a crystallized product
Phase diagram
Chemical Changes in Materials
The chemical changes to materials in a process take the form of
chemical reactions. These chemical reactions can take several
forms:
 Compounds break apart and produce elements.
 Compounds break apart to form smaller compounds. FCC
 Elements combine to form compounds. polymerization
 Compounds combine with other compounds to produce new
compounds. Isomerization / branching, alkalization reactions
 THE LAW OF CONSERVATION OF
MATERIAL
Material cannot be created or
destroyed, but it can be changed in form
by physical or chemical actions.
Overall Material Balance
 Overall balances can be used by operators to take a quick look at the process as
a whole to verify that all of the materials entering a process are accounted for in
the system. Overall balances can take different forms, depending on what
information is available:

Mass In = Mass Out

Moles In= Moles Out
Volume In = Volume Out
 Note 1: Due to the inherent issues associated with accurately measuring
volume and the impacts of process conditions on volume, it is often difficult to
balance a system on a volume basis. However, volume balances can be used on
a limited basis as indicators for process conditions.

 Note 2: A mole represents a specific number (6.022 x 1023) of molecules or

atoms.

The simplest forms of an overall material balance are:

 The volume balance, which is the least accurate.
 The mass (moles or weight) balance, which is the most accurate.
In a component balance, one chemical component is followed throughout a
process system. This type of specialized balance is used to:
 Help track reaction products and byproducts.
 Evaluate the quality of various product streams in both reactive and non-
reactive systems.

In order to perform a component balance, it is necessary to have access to

composition data from either on-line analyzers or laboratory analysis. A
component balance can be represented by the following formula:

Mass (Component A) In + Mass (Component A) Produced = Mass (Component

A) Consumed + Mass (Component A) Out
Why doing mass balance?
 Mass balances are used to determine where the product is going. If the mass
into a unit does not equate to the mass out of the unit, then there is a problem
with the process.
 When performing a material balance, the first step is to obtain the flows of all
inlet and outlet streams to the process. These streams are typically measured
by flow meters and characterized by laboratory data.
 Next, the flow meters are corrected for actual flowing temperature and
pressure. Each meter is initially calibrated using a base condition specific
gravity. As the unit runs, the actual process stream strays from these base
conditions. Therefore, the flow meter data must be adjusted to account for
actual operating conditions.
 The actual temperature and pressure of the process stream is used to adjust the
specific gravity of the fluid during operation. A factor is calculated and then
used to adjust the flow measurement. This adjusted flow measurement is called
the “corrected data”. This is typically given in a volume or a mass basis.

 All of the input and output streams on a mass basis are totaled. The totals are
then used in the following equation:

 (Total Mass Out / Total Mass In)*100 = Mass Balance Closure

Batch process:
 Raw materials are fed into the process
 Process runs for x length of time
 NO mass ENTERS or LEAVES while the process is running
 Energy inputs may take place (heating/cooling etc.)
 Product produced is removed at the END of the process

Semibatch process:
A semibatch process does not comply fully to either “batch” or “continuous”
processes as per their definitions.
Continuous process:
Raw materials continuously ENTERS and product continuously LEAVES the
process
Steady-state operation:
Values of all variables associated with the process do not change with time. That
is, at any given location in the process, the values of temperature, pressure,
composition, flow rates, etc. are independent of time.
Even though a process may be steady state, it is important to realize that
temperature, flow rates, or other variables may, (typically do), change between
locations (e.g. from one process stream to another)
Transient or unsteady-state operation:
 When process variables change with time.
A process must be either steady-state or transient.
 Batch and semi-batch processes must be transient.
 Continuous processes may be transient or steady-state.
Basic process types

Type 1: Single reactor product stream without separation

See previous example – PEG production

Type 2: Multiple reactor products without separation

Aniline production: C6H5Cl + 2NH3  C6H5NH2 + NH4Cl

Product in phase 1
Feed
Reactor Product in phase 2
Basic process types

Type 3: Single reactor product stream with separation

CH3OH + NH3  CH3NH2 + H2O

The reaction takes place in the vapour phase at 350 to 4500

o
C and 200 psi pressure
Basic process types

Type 4: Multiple separations involving reactor feed and

product streams
H2 from methane:
CH4 + 2 H2O  CO2 + 4 H2
Methane feed, obtained from natural gas, is de-sulphurised by
contact with activated carbon. The CO2 in the product stream
is removed by scrubbing with a monoethanolamine solution.
Basic process types

Type 5: Reactor with recycle

Haber process
Types of balances

Differential balances:
Application: Continuous processes
Terms used in a differential material balance are expressed as
RATES
• Rate of input
• Rate of output
• Rate of accumulation
Units: moles/s or kg/s
Types of balances

Integral balances:
Application: Batch processes
Terms used in batch material balances expressed as
AMOUNTS
Process is sealed at the beginning: Reaction/transformation of
the input/feed materials takes place.
Process opened and content removed.
INPUT: Amount fed into the system at the start of the process
OUTPUT: Amount removed including both products and
unconverted reactants.
Process: INPUT REACTION OUTPUT
Units: Molar or mass
Types of balances and terms used

Generation/consumption:
Amounts produced/consumed during the time between the
start and the end of the process.

Accumulation is the amount left behind in the process (this is

zero if all materials are removed).
The Material balance equation

Closed Systems:
Closed to mass flow – not energy flow
Accumulation = Generation

No Generation (No chemical reaction):

Some things enter and leave a system unchanged – very
useful for mass balancing (no generation term)
Accumulation = In – Out

Steady state systems:

Refers to systems that does not accumulate anything
In – Out + Generation – Consumption = 0
The Material balance equation

Representation:

Accumulation = In – Out + Generation - Consumption

Material In Material Out

System
(Accumulation or
Consumption)
 Mass Balance

 
Volumetric flow rates to mass flows
 Definition of Volumetric flow rate (Vf)

 The relation between the volume of a gas or liquid passing through a fixed
point in a process within a given amount of time.
 Volumetric flow rates to mass flows

 
Volumetric flow rates to mass flows

Why do we convert volumetric flow rates to mass flow rates

1. Volumetric flowrates are not conserved
2. Volumetric flow rates cannot be split into components as
in the case with mass or moles
3. Very uncommon to measure anything in volume fractions
(rate)
Therefore: Convert Volumetric flowrates to either mass or
mole flow rates using the following equations:
 Velocities to mass flows

 
Procedure for mass balance calculations

 Step 1: Draw and label the PFD

 Step 2: Select the basis for the calculation
 Step 3: Convert all units to a consistent basis
 Step 4: Set up the mass balance equations
 Step 5: Do the calculations
 Step 6: Check the calculation
Example Calculation

An aqueous solution of sodium hydroxide contains 20%

NaOH by mass and is diluted to an 8% NaOH solution by
diluting a stream of the 20% solution with a stream of pure
water.

Calculate the following ratios:

 g pure H2O that must be fed for every g of feed solution,
 and g product solution produced for every g feed solution.
Example Calculation

An aqueous solution of sodium hydroxide contains 20%

NaOH by mass and is diluted to an 8% NaOH solution by
diluting a stream of the 20% solution with a stream of pure
water.

Step 1: Draw and Label the PFD

Example Calculation

An aqueous solution of sodium hydroxide contains 20%

NaOH by mass and is diluted to an 8% NaOH solution by
diluting a stream of the 20% solution with a stream of pure
water. Basis: 1g feed

Step 1: Draw and Label the PFD

20 % NaOH sln 8 %NaOH soln

100% water
Example Calculation

An aqueous solution of sodium hydroxide contains 20%

NaOH by mass and is diluted to an 8% NaOH solution (by
mass) by diluting a stream of the 20% solution with a
stream of pure water.

Step 1: Draw and Label the PFD

20 % NaOH sln 8 % NaOH sln

0.2 g NaOH/g feed sln 0.08 g NaOH/g feed sln
Thus x g H20/g feed sln
0.8 g H20/g feed sln (total = y g)
(total = 1 g)

100% water = x g water

Example Calculation

An aqueous solution of sodium hydroxide contains 20%

NaOH by mass and is diluted to an 8% NaOH solution (by
mass) by diluting a stream of the 20% solution with a
stream of pure water.

Step 1: Draw and Label the PFD

20 % NaOH sln 8 % NaOH sln

F1 0.2 g NaOH/g feed sln
F3
NaOH: 0.08(100+x)
Thus H2O: 0.92(100+x)
0.8 g H20/g feed sln
(total = 1 g)

F2 100% water = x g water

Example Calculation

An aqueous solution of sodium hydroxide contains 20%

NaOH by mass and is diluted to an 8% NaOH solution by
diluting a stream of the 20% solution with a stream of pure
water.

Step 2: Select the basis for calculation

 g pure H2O that must be fed for every g of feed solution,
 and g product solution produced for every g feed solution.
Example Calculation – Method 1

An aqueous solution of sodium hydroxide contains 20% NaOH by

mass and is diluted to an 8% NaOH solution by diluting a stream of
the 20% solution with a stream of pure water. Basis: 100 g feed

MASS IN = MASS OUT

Overall: F1 +F2 = F3
Known: F1 = 100 g
Thus: 100g + x g = F3 (1)
NaOH:
0.2(100)F1 = 0.08(100+x) (2)
H2O:
0.8(100)F1 + xF2 = 0.92(100+x) (3)
From (2)
20 g = 8 g + 0.08x
X = 150 g
Test: Y = X + 100 g = 150 + 100 = 250 g
Example Calculation – Method 2

An aqueous solution of sodium hydroxide contains 20%

NaOH by mass and is diluted to an 8% NaOH solution by
diluting a stream of the 20% solution with a stream of pure
water. Basis 100 g

MASS IN = MASS OUT

TOT IN: 20 g NaOH + 80 g H20 + x g H20 = 100 g sln + x g H20
TOT OUT: 20 g NaOH + 80 g H20 + x g H20 = y total g out
FINAL: 100 g sln + x g H20 = y total g solution out

KNOWN: 20 g NaOH = 8% of y or (0.08 x y)

So… Solve for y
y g total solution = 20 g NaOH / (8/100)
y = 250 g total mass of solution
Example Calculation

An aqueous solution of sodium hydroxide contains 20%

NaOH by mass and is diluted to an 8% NaOH solution by
diluting a stream of the 20% solution with a stream of pure
water.

MASS IN = MASS OUT

TOT IN: 20 g NaOH + 80 g H20 + x g H20 = 100 g sln + x g H20 eq 1
TOT OUT: 20 g NaOH + 80 g H20 + x g H20 = y total g out eq 2
FINAL: 100 g sln + x g H20 = y total g solution out eq 3

SUBSTITUTE Y INTO EQ 3: y = 250 g total mass of solution

100 g sln + x g H20 = 250 total g solution out
x g H20 in = 250 g total out – 100 g total in
= 150 g water was fed into the system to dilute the NaOH
solution from 20% to 8%
Example Calculation

An aqueous solution of sodium hydroxide contains 20%

NaOH by mass with a feed rate of 1000 g/min and is
diluted to an 8% NaOH solution by diluting a stream of the
20% solution with a stream of pure water.
Questions:
What would the product stream and the diluent (water) flow
rates be respectively?
Example Calculation

Step 1: PFD
Step 2: Basis of equation
Flow rate g/min (not grams fed)
If the flow rate of the incoming stream is 1000 g/ min then the flow rate
for each fraction may be calculated by multiplying the fraction by the
flow rate. The total = 1000 g/min
Flow rate: 1000 g/min
Example Calculation

Flow rate: 1000 g/min

Incoming stream:
(1000 g/min x 0.8 g H20/g sln) + (1000 g/min x 0.2 g NaOH/g sln)
= 800 g/min + 200 g/min
= 1000 g/min flow for 20% NaOH sln
Diluent:
1000 g/min x 1.5 g H20/g =1500 g/min
Product stream:
2.5 g/g total solution of which:
0.8 g NaOH/g solution
0.2 + 1.5 g H20/g solution
Flow rate: 1000 g/min
NaOH: 0.8 g/g x 1000 g/min = 800 g/min
H20: (0.2 + 1.5 g/g) x 1000 g/min = 1700 g/min
Total: 800 g/min + 1700 g/min = 2500 g/min
Check: Total in = total out thus: 1000g/min +1500 g/min = 2500
Example Calculation

Do calculations
 We know that Eq 1 contains two unknowns but Eq 2 only
one
 Solve for y by using Eq 2
 y = 2500 g/min
 Insert value into Eq 1 and solve for x
 x = 1500 g/min
 Calculate g pure H2O that must be fed for every g of feed
solution: 1.5 g pure water/1 g 20% NaOH sln
 Calculate g product solution produced for every g feed
solution: 2500/1000 = 2.5 g/g
Example 2: Calculation

A mixture containing 45% benzene (B) and 55% toluene (T) by

mass is fed to a distillation column. An overhead stream of 95
wt% B is produced, and 8% of the benzene fed to the column
leaves in the bottom stream. The feed rate is 2000 kg/h.
Determine the overhead flow rate and the mass flow rates of
benzene and toluene in the bottom stream.
Example 2: Calculation

A mixture containing 45% benzene (B) and 55% toluene (T) by mass is fed
to a distillation column. An overhead stream of 95 wt% B is produced, and
8% of the benzene fed to the column leaves in the bottom stream. The feed
rate is 2000 kg/h. Determine the overhead flow rate and the mass flow
rates of benzene and toluene in the bottom stream.

Step 1: Draw and label BFD

Example 2: Calculation

Step 1: Draw and label BFD

Overhead (x kg/hr)
0.95 kg B/kg
0.05 kg T/kg

Feed (2000 kg/hr)

0.45 kg B/kg
S
0.55 kg T/kg
Bottoms (Contain 8%
of all B in Feed) (q
kg/hr)
Y kg B/hr
Z kg T/hr
Example 2: Calculation

A mixture containing 45% benzene (B) and 55% toluene (T) by mass is fed
to a distillation column. An overhead stream of 95 wt% B is produced, and
8% of the benzene fed to the column leaves in the bottom stream. The feed
rate is 2000 kg/h. Determine the overhead flow rate and the mass flow
rates of benzene and toluene in the bottom stream.

Step 2: Select basis for calculation

Simply use the feed rate 2000 kg/hr

Example 2: Calculation

A mixture containing 45% benzene (B) and 55% toluene (T) by mass is fed
to a distillation column. An overhead stream of 95 wt% B is produced, and
8% of the benzene fed to the column leaves in the bottom stream. The feed
rate is 2000 kg/h. Determine the overhead flow rate and the mass flow
rates of benzene and toluene in the bottom stream.

Step 3: Convert units to consistent basis

 Example 2: Calculation

Step 3: Convert units to consistent basis

All the units are in kg or kg/hr

Since we are working in mass flow rates, we can convert the proportions of
B and T in the feed, overhead and bottoms to mass flows:

Feed:
B: 0.45 kg/kg * 2000 kg/hr = 900 kg/hr
T: 0.55 kg/kg * 2000 kg/hr = 1100 kg/hr

Overhead:
B: 0.95 kg/hr * x kg/hr = 0.95x kg/hr
T: 0.05x kg/hr

Bottoms:
B: y kg/hr
T: z kg/hr
Example 2: Calculation

A mixture containing 45% benzene (B) and 55% toluene (T) by mass is fed
to a distillation column. An overhead stream of 95 wt% B is produced, and
8% of the benzene fed to the column leaves in the bottom stream. The feed
rate is 2000 kg/h. Determine the overhead flow rate and the mass flow
rates of benzene and toluene in the bottom stream.

Step 4: Set up mass balance equations

Example 2: Calculation

Step 4: Set up mass balance equations

We have two species for which we can set up two individual species mass
balances and also one for the overall mass balance:

Benzene balance:
Benzene in = Benzene out
(900 kg/hr) = 0.95x kg/hr + y kg/hr

Toluene balance:
Toluene in = Toluene out
1100 kg/hr = 0.05x kg/hr + z kg/hr

Overall mass balance:

Total mass in = Total mass out
2000 kg/hr = x kg/hr + q kg/hr
Example 2: Calculation

A mixture containing 45% benzene (B) and 55% toluene (T) by mass is fed
to a distillation column. An overhead stream of 95 wt% B is produced, and
8% of the benzene fed to the column leaves in the bottom stream. The feed
rate is 2000 kg/h. Determine the overhead flow rate and the mass flow
rates of benzene and toluene in the bottom stream.

Step 5: Do the calculations

Example 2: Calculation

Step 5: Do the calculations

You should note that there are three mass balance equations but FOUR
unknowns: Overhead flow (x), Bottoms flow (q) and proportions of B and T
in bottom stream (y and z).
We can solve only three unknowns from three equations, hence the fourth
one must be solved from other information provided.
The bottom stream contains 8% of all the benzene fed:
(2000 kg/hr * 0.45 kg/kg * 8/100) = 72 kg/hr = y
Substitute into benzene balance:
900 kg/hr = 0.95x kg/hr + 72 kg/hr => x = 872 kg/hr

The rest is easy:

q = 1128 kg/hr
z = 1056 kg/hr
Example 2: Calculation

Step 6: Check the calculations

Benzene balance
900 kg/hr = (0.95 * 872) kg/hr + 72 kg/hr = 900 kg/hr

Toluene balance
1100 kg/hr = ((q – y) + 0.05x) kg/hr = (1128 – 72) + (0.05 * 872) = 1100
kg/hr

Overall balance
2000 kg/hr = (q + x) kg/hr = (872 + 1128) = 2000 kg/hr
Examples of material balances
Mixer
An aqueous solution of sodium hydroxide contains 20% NaOH by mass and is
diluted to an 8% NaOH solution by diluting a stream of the 20% solution with
a stream of pure water. Draw a simple block flow diagram (BFD) representing
this process.
Divider
An intimately mixed solution of water and xylene containing 6% xylene by mass
flows into a phase separator where the xylene is completely separated from the
water. Draw a PFD representing this process.
Separator / fractionator / distillation
A mixture containing 45% benzene (B) and 55% toluene (T) by mass is fed to a
distillation column. An overhead stream of 95 wt% B is produced, and 8% of
the benzene fed to the column leaves in the bottom stream. Draw a PFD
representing this process.
Reactor
Ethylene glycol (100%) and ethylene oxide (100%) is reacted in a CSTR
(Continuous stirred tank reactor) to produce PEG (polyethylene glycol) which
is removed continuously from the reactor as a 85% solution in ethylene glycol.
Draw a PFD representing this process
 Problem 5.1

A salt solution is to be concentrated by evaporating the water

in a salt pan, with a condensing surface above it to gather the
evaporated water. Suppose 1200g of salt solution are emptied
into the pan. Once all the water is evaporated, the salt is
weighed and found to weigh 100g. What percent of the original
solution was water?
x g Water Mass in = Mass Out
1200g Salt Soln = 100 g salt + x g Water
x = 1200 – 100 g
= 1100 g water
1200g Salt
Solution Evaporator
% Water = 1100 g/1200 g * 100
= 91.7 %
100g Salt
Problem 5.2

(a) In a stone quarry, limestone is to be crushed and poured into

moulds for manufacture of floor tiles. Suppose that a limestone
company uses three trucks, each of which is capable of carrying
3000 kg of limestone. The quarry itself is 20 miles away from the
processing plant, and the trucks get there at an average speed of
30 miles/hour. Once at the plant, the limestone is ground into fine
powder and then melted and poured into the moulds. If each of the
resulting slabs weighs 2 kg and the plant operates 24 hours a day,
how many slabs can the company make in a day?
(b) How could this plant become more efficient? Plot the number of
slabs the company can make as a function of distance from the
quarry and capacity of the trucks. What factors might keep the
company from simply moving as close to the quarry as possible
and using the largest trucks possible?
Problem 5.2

Step 1
3000 kg @ 30 miles/hr over 20 miles

3000 kg @ 30 miles/hr over 20 miles Y slabs/24h @ 2kg/slab

3000 kg @ 30 miles/hr over 20 miles

Step 2: Basis for calculation (total input/h)

Step 3: Convert units

Convert 3000 kg @ 30 miles/h over 20 miles to total kg over 24 h
20 miles/30 miles/h = 20 miles * 1/30 h/miles = 0.667 h
Mass/24 h = 24/0.667h * 3000 kg
= 36 * 3000 kg/24hr = 108 000 kg/24hr

Step 4: Mass balance

Mass in = mass out
3 * 108000 kg/24hr = 3 * 108000 kg/24 hr

Step 5: No of slabs = 324000 kg/24h/2 kg = 162 000 slabs

Problem 5.2

2500000

2000000
M
a
s 1500000
s
/ 1000000
2 Series1
4
h 500000

0
0 5 10 15 20 25
Distance from Quarry (miles)

500000
450000
400000
M
a 350000
s 300000
s 250000
/
2 200000
Series1
4 150000
h
100000
r
50000
0
2000 4000 6000 8000 10000 12000 14000
Truck capacity (kg)
Problem 5.3

Air is bubbled through a container of liquid hexane at a rate of 0.100

kmol/min. It then leaves the container, such that the output gas contains
10.0 mole % hexane vapour. Assume that air is insoluble in liquid hexane.
What is the time required to vaporize 10.0 m3 of the hexane?

Step 1:
Hexane
Air (0.1 kmol/min) (10 m3) Hexane/Air (10
mol %)

Required: Molecular mass of hexane = 86.18 g/mol

Density of hexane = 0.6548 g/cm3
Average molecular mass of air = 0.79 * 28 + 0.21*32 = 28.84 g/mol
Problem 5.3

Hexane
Air (0.1 kmol/min) (10 m3) Hexane/Air (10
mol %)
Step 2: Convert 10 m3 hexane to moles:
10 m3 * 0.6548 kg/m3 = (6.548 kg * 1000 g/kg)/(86.18 g/mol) = 75.98 moles
Step 3: Mole balances
Hexane: Moles in = Moles out = 75.98 moles Hexane
Air: x moles Air = (75.98 moles hexane/0.1 mol % (hexane in air)) – 75.98
moles hexane
Step 4: Calculate
x = 759.8 moles air – 75.98 moles Hexane = 683.82 moles air = 0.684 kmol
Time (@ flow of 0.1 kmol/min) = 0.684/0.1 = 6.84 min
Step 5: Check
(75.98/759.8) * 100 = 10 %
6.84 min * 0.1 kmol/min = 0.684 kmol air
Problem 5.4

You are asked to make 1,000 kg of the mixed acid containing 60 wt%
H2SO4, 32 wt% HNO3, and 8 wt% water, by mixing the following three
solutions:
i) mixed acid containing 11.3% HNO3, 44.4% H2SO4, and 44.3% water,
ii) 90% HNO3 aqueous solution, and
iii) 98% H2SO4 aqueous solution
Calculate mass of Streams i, ii, and iii.

x kg (i) (0.113 kg/kg N; 0.444

kg/kg H; 0.443 kg/kg W)
1000 kg acid
600 kg Sulfuric
y kg (ii) (0.90 kg/kg N; 0.10 320 kg Nitric
kg/kg W) 80 kg water
z kg (iii) (0.98 kg/kg H; 0.02
kg/kg W)
Problem 5.4

x kg (i) (0.113 kg/kg N; 0.444

kg/kg H; 0.443 kg/kg W)
1000 kg acid
600 kg Sulfuric
y kg (ii) (0.90 kg/kg N; 0.10 320 kg Nitric
kg/kg W) 80 kg water

z kg (iii) (0.98 kg/kg H; 0.02

kg/kg W)

Step 2: Conversions (none)

Step 3: Basis (1000 kg product)
Step 4: Mass balances
N: 0.113x + 0.90y = 320 kg
S: 0.444x + 0.98z = 600 kg
W: 0.443x + 0.10y + 0.02z = 80 kg
Overall: x + y + z = 1000 kg
.
Problem 5.4

Step 4: Mass balances

N: 0.113x + 0.90y = 320 kg
S: 0.444x + 0.98z = 600 kg
W: 0.443x + 0.10y + 0.02z = 80 kg
Overall: x + y + z = 1000 kg

Step 5: Calculate
From S: z = (600 – 0.444x)/0.98 = 612.24 – 0.453x
Into W: 0.443x +0.10y + 0.02(612.24 – 0.453x) = 80
0.443x – 0.009x + 0.10y + 12.24 = 80
W’: 0.434x + 0.10y = 67.76
9*W’ – N: 3.793x = 289.84
x = 76.4 Kg
Thus: y = 346.0 kg
z = 577.6 kg
Problem 5.5

Stream 1, containing only substance A, is mixed with Stream 2,

which contains substances A & B, at the mixing point. The flow
rates of Streams 1 & 2 are 60.0 & 30.0 kg/h, respectively. The
mass fraction of A in the Stream 2 is 0.35. Determine the
composition of the output stream.

(i) (A only @ 60 kg/h)

Mixing (iii) (x A + yB 90 kg/h)

Point
(ii) (0.35kg A/kg @ 30
kg/h)
Problem 5.5

(X) (A only @ 60 kg/h)

Mixing (Z) (x A + yB 90 kg/h)

Point
(Y) (0.35kg A/kg @ 30
kg/h)

Step 2: Conversions (none)

Step 3: Basis (60kg/h of stream 1)
Step 4: Mass balances
A: (X + 0.35Y) kg/h = xZ kg/h
B: 0.65Y = yZ kg/g
O: X + Y = Z (kg/h)
Problem 5.5

Step 4: Mass balances

A: (X + 0.35Y) kg/h = xZ kg/h
B: 0.65Y = yZ kg/g
O: X + Y = Z (kg/h)

Step 5: Calculate
From A: 60 kg/h + 0.35 * 30 kg/h = x * 90 kg/h
70.5 kg/h/90 kg/h = x = 0.78

From B: 0.65 * 30 kg/h = y * 90 kg/h

19.5 kg/h/90 kg/h = y = 0.22

Step 6: Check
X+Y=Z
60 + 30 = 0.78 * 90 + 0.22 * 90
90 = 90
Problem 5.6

An evaporator is used to concentrate a dilute 4 wt% caustic soda (NaOH)

solution to 25 wt%. Calculate the amount of water to be evaporated per 100
kg of feed.
Water

NaOH (4% m/m)

0.04 kg/kg NaOH Evaporator

NaOH (25% m/m)

0.25 kg/kg NaOH
Problem 5.6

Step 2: Conversions (None)

Step 3: Basis (100 kg of Feed)

Step 4: Balances
NaOH: 0.04F = 0.25 P
Water: 0.96F = 1W + 0.75P
O: F = P + W

Step 5: Calculate
From NaOH: 0.04 * 100 = 4 kg/h NaOH = 0.25P
P = 4/0.25 = 16 kg/h product
From Water: 96 = W + 0.75 *16 (kg/h)
W = 84 kg/h
Water evaporated/kg feed
84/100 = 0.84 kg water/kg feed
Problem 5.7

Membrane separation is a technology for separating gases. A nano-porous

membrane is used to concentrate the amount of oxygen in the product
stream as illustrated in the PFD below. If the waste stream contains 75% of
the moles of the input stream, what is the molar composition (percentage)
of the waste stream?

High P side
79 mole% N2 Low P side
21 mole% O2 Membrane 70 mole% N2
30 mole% O2

Waste (75 %
of input)
Problem 5.7

Step 2: Basis for calculation (100 moles air)

Step 3: Conversions (none)

Step 4: Mass balances

N: 79 moles = 0.7 * 25 moles + x * 75 moles
O: 21 moles = 0.3 * 25 moles + y * 75 moles

Step 5: Calculate
From N: 79 = 17.5 +75x
x = (79 – 17.5)/75 = 0.82
From O: 21 = 7.5 +75y
y = (21 – 7.5)/75 = 0.18

Step 6: Check
(.82*75 + .18*75) + (.7*25 +.3*25) = (61.5 + 13.5) +(17.5 + 7.5)
= 75 + 25
Kinetics
 Studies the rate at which a chemical process occurs.
 Besides information about the speed at which reactions occur, kinetics also
sheds light on the reaction mechanism (exactly how the reaction occurs).
Outline: Kinetics
Reaction Rates How we measure rates.

How the rate depends on amounts

Rate Laws of reactants.
How to calc amount left or time to
Integrated Rate Laws reach a given amount.
How long it takes to react 50% of
Half-life reactants.

Arrhenius Equation How rate constant changes with T.

Link between rate and molecular

Mechanisms scale processes.
Factors That Affect Reaction Rates
 Concentration of Reactants
• As the concentration of reactants increases, so does the likelihood
that reactant molecules will collide.
 Temperature
• At higher temperatures, reactant molecules have more kinetic
energy, move faster, and collide more often and with greater energy.
 Catalysts
• Speed rxn by changing
mechanism.
 Reaction Rates

Rxn Movie

Rates of reactions can be determined by monitoring

the change in concentration of either reactants or
products as a function of time. [A] vs t
Reaction Rates
C4H9Cl(aq) + H2O(l)  C4H9OH(aq) + HCl(aq)
[C4H9Cl] M
In this reaction, the
concentration of butyl
chloride, C4H9Cl, was
measured at various
times, t.
Reaction Rates
C4H9Cl(aq) + H2O(l)  C4H9OH(aq) + HCl(aq)
Average Rate, M/s
The average rate of the
reaction over each
interval is the change in
concentration divided by
the change in time:
Reaction Rates
C4H9Cl(aq) + H2O(l)  C4H9OH(aq) + HCl(aq)

 Note that the average rate

decreases as the reaction
proceeds.
 This is because as the
reaction goes forward, there
are fewer collisions between
reactant molecules.
Reaction Rates
C4H9Cl(aq) + H2O(l)  C4H9OH(aq) + HCl(aq)

 A plot of concentration vs.

time for this reaction yields
a curve like this.
 The slope of a line tangent
to the curve at any point is
the instantaneous rate at
that time.
Reaction Rates
C4H9Cl(aq) + H2O(l)  C4H9OH(aq) + HCl(aq)

 Thereaction slows down

with time because the
concentration of the
reactants decreases.
Reaction Rates and Stoichiometry
C4H9Cl(aq) + H2O(l)  C4H9OH(aq) + HCl(aq)

 In
this reaction, the ratio of
C4H9Cl to C4H9OH is 1:1.
 Thus,the rate of
disappearance of C4H9Cl is
the same as the rate of
appearance of C4H9OH.

-[C4H9Cl] [C4H9OH]
Rate = =
t t
Reaction Rates and Stoichiometry

 What if the ratio is not 1:1?

H2(g) + I2(g)  2 HI(g)

• Only 1/2 HI is made for each H2 used.
Reaction Rates and Stoichiometry

 To generalize, for the reaction

aA + bB cC + dD

Reactants (decrease) Products (increase)

Concentration and Rate
Each reaction has its own equation that gives its rate as a function of reactant
concentrations.

this is called its Rate Law

To determine the rate law we measure the rate at different
starting concentrations.
Concentration and Rate

Compare Experiments 1 and 2:

when [NH4+] doubles, the initial rate doubles.
Concentration and Rate

Likewise, compare Experiments 5 and 6:

when [NO2-] doubles, the initial rate doubles.
Concentration and Rate

This equation is called the rate law,

and k is the rate constant.
Rate Laws
 A ratelaw shows the relationship between the reaction rate and
the concentrations of reactants.
• For gas-phase reactants use PA instead of [A].

k is a constant that has a specific value for each reaction.

 The value of k is determined experimentally.

“Constant” is relative here-

k is unique for each rxn
k changes with T (section 14.5)
Rate Laws
 Exponents tell the order of the reaction with respect
to each reactant.
 This reaction is

First-order in [NH4+]
First-order in [NO2−]
 The overall reaction order can be found by adding
the exponents on the reactants in the rate law.
 This reaction is second-order overall.
Integrated Rate Laws
Consider a simple 1st order rxn: A  B

Differential form:

How much A is left after time t? Integrate:

Integrated Rate Laws
The integrated form of first order rate law:

Can be rearranged to give:

[A]0 is the initial concentration of A (t=0).

[A]t is the concentration of A at some time, t,
during the course of the reaction.
 Integrated Rate Laws
Manipulating this equation produces…

…which is in the form y = mx + b

First-Order Processes

If a reaction is first-order, a plot of ln [A]t vs. t will yield a straight line

with a slope of -k.

So, use graphs to determine rxn order.

First-Order Processes
Consider the process in
which methyl isonitrile is
converted to acetonitrile.

CH3NC CH3CN

How do we know this

is a first order rxn?
 First-Order Processes
CH3NC CH3CN

This data was collected

for this reaction at
198.9°C.

Does
rate=k[CH3NC]
for all time intervals?
First-Order Processes

 When ln P is plotted as a function of time, a

straight line results.
• The process is first-order.
• k is the negative slope: 5.1  10-5 s-1.
Second-Order Processes
Similarly, integrating the rate law for a process that
is second-order in reactant A:

Rearrange, integrate:

also in the form y = mx + b

Second-Order Processes

So if a process is second-order in A, a plot of 1/[A] vs. t will yield a

straight line with a slope of k.

First order:

If a reaction is first-order, a plot of ln [A]t vs. t will yield

a straight line with a slope of -k.
 Determining rxn order
The decomposition of NO2 at 300°C is described by
the equation
NO2 (g) NO (g) + 1/2 O2 (g)
and yields these data:
Time (s) [NO2], M
0.0 0.01000
50.0 0.00787
100.0 0.00649
200.0 0.00481
300.0 0.00380
 Determining rxn order
Graphing ln [NO2] vs. t yields:
• The plot is not a straight
line, so the process is not
first-order in [A].
Time (s) [NO2], M ln [NO2]
0.0 0.01000 -4.610
50.0 0.00787 -4.845
Does not fit:
100.0 0.00649 -5.038
200.0 0.00481 -5.337
300.0 0.00380 -5.573
 Second-Order Processes
A graph of 1/[NO2] vs. t
gives this plot.

Time (s) [NO2], M 1/[NO2]

• This is a straight
0.0 0.01000 100 line. Therefore, the
50.0 0.00787 127 process is second-
100.0 0.00649 154 order in [NO2].
200.0 0.00481 208
300.0 0.00380 263
Half-Life
 Half-life is defined as
the time required for
one-half of a reactant to
react.
 Because [A] at t1/2 is
one-half of the original
[A],
[A]t = 0.5 [A]0.
Half-Life
For a first-order process, set [A]t=0.5 [A]0 in
integrated rate equation:

NOTE: For a first-order

process, the half-life does
not depend on [A]0.
Half-Life- 2nd order
For a second-order process, set
[A]t=0.5 [A]0 in 2nd order equation.
Outline: Kinetics
First order Second order Second order

Rate
Laws

Integrate
d Rate complicated
Laws

Half-life complicated
Temperature and Rate
 Generally, as temperature
increases, so does the reaction
rate.
 This is because k is
temperature dependent.
Activation Energy
 Inother words, there is a minimum amount of energy
required for reaction: the activation energy, Ea.
 Justas a ball cannot get over a hill if it does not roll up the
hill with enough energy, a reaction cannot occur unless the
molecules possess sufficient energy to get over the
activation energy barrier.
Reaction Coordinate Diagrams

It is helpful to
visualize energy
changes throughout a
process on a reaction
coordinate diagram
like this one for the
rearrangement of
methyl isonitrile.
 Reaction Coordinate Diagrams
 Itshows the energy of the
reactants and products (and,
therefore, E).
 The high point on the
diagram is the transition
state.

• The species present at the transition state is

called the activated complex.
• The energy gap between the reactants and the
activated complex is the activation energy
barrier.
Maxwell–Boltzmann Distributions

 Temperature is
defined as a measure
of the average kinetic
energy of the
molecules in a
sample.

• At any temperature there is a wide

distribution of kinetic energies.
Maxwell–Boltzmann Distributions

 As the temperature
increases, the curve
flattens and broadens.
 Thus at higher
temperatures, a larger
population of
molecules has higher
energy.
Maxwell–Boltzmann Distributions
 If
the dotted line represents the activation energy, as
the temperature increases, so does the fraction of
molecules that can overcome the activation energy
barrier.

• As a result, the
reaction rate
increases.
Maxwell–Boltzmann Distributions
This fraction of molecules can be found through the expression:

where R is the gas constant and T is the temperature in Kelvin .

 Arrhenius Equation
Svante Arrhenius developed a mathematical relationship between k and Ea:

where A is the frequency factor, a number that represents the likelihood that
collisions would occur with the proper orientation for reaction.
 Arrhenius Equation
Taking the natural
logarithm of both sides,
the equation becomes

1
RT
y = mx + b
When k is determined experimentally at
several temperatures, Ea can be calculated
from the slope of a plot of ln k vs. 1/T.
Outline: Kinetics
First order Second order Second order

Rate
Laws

Integrate
d Rate complicated
Laws

Half-life complicated

k(T)
Reaction Mechanisms
The sequence of events that describes the actual process by which reactants
become products is called the reaction mechanism.
Reaction Mechanisms
 Reactions may occur all at once or through several discrete steps.
 Each of these processes is known as an elementary reaction or elementary
process.
Reaction Mechanisms

• The molecularity of a process tells how many

molecules are involved in the process.

• The rate law for an elementary step is written directly

from that step.
Multistep Mechanisms

 In a multistep process, one of the steps will be

slower than all others.
 The overall reaction cannot occur faster than this
slowest, rate-determining step.
Slow Initial Step
NO2 (g) + CO (g)  NO (g) + CO2 (g)

 The rate law for this reaction is found experimentally to

be
Rate = k [NO2]2
 CO is necessary for this reaction to occur, but the rate of
the reaction does not depend on its concentration.
 This suggests the reaction occurs in two steps.
 Slow Initial Step
 A proposed mechanism for this reaction is
Step 1: NO2 + NO2  NO3 + NO (slow)
Step 2: NO3 + CO  NO2 + CO2 (fast)
 The NO3 intermediate is consumed in the second step.
 AsCO is not involved in the slow, rate-determining step, it does not
appear in the rate law.
Fast Initial Step

 The rate law for this reaction is found (experimentally) to be

 Because termolecular (= trimolecular) processes are rare, this rate law

suggests a two-step mechanism.
Fast Initial Step
 A proposed mechanism is

Step 1 is an equilibrium-
it includes the forward and reverse reactions.
Fast Initial Step

 The rate of the overall reaction depends upon the rate of the slow step.
 The rate law for that step would be

 But how can we find [NOBr2]?

Fast Initial Step
 NOBr2 can react two ways:
• With NO to form NOBr
• By decomposition to reform NO and Br2
 The reactants and products of the first step are in equilibrium with each other.
 Therefore,
Ratef = Rater
Fast Initial Step

 Because Ratef = Rater ,

k1 [NO] [Br2] = k−1 [NOBr2]

Solving for [NOBr2] gives us

k1
[NO] [Br2] = [NOBr2]
k−1
Fast Initial Step

Substituting this expression for [NOBr2] in the rate law for the rate-
determining step gives
Catalysts
 Catalysts increase the rate of a reaction by
decreasing the activation energy of the reaction.
 Catalysts change the mechanism by which the
process occurs.
Catalysts

One way a catalyst

can speed up a
reaction is by
holding the
reactants together
and helping bonds
to break.
Catalysts in Hydrocarbon Processing
 Describe the purpose of a catalyst
 Describe the action of a catalyst
 Describe catalyst degradation
Introduction
Catalysts determine the rate at which a reaction occurs and the factors that
affect their speed. They can also improve processes economically and
functionally by lowering necessary operating temperatures which in turn
minimizes the operating severity.
Purpose of a Catalyst
 Describe why catalysts are needed in reactions
 Describe reaction effectiveness
 Describe how catalysts increase the reaction rate
 Elements or compounds with defined properties are converted by chemical
reactions into other elements or compounds with different properties. The rate
at which these reactions occur is very important to the chemical industry
Why a catalysts are needed
How reactions happen
Chemical reactions usually occur between:
 Gaseous substances.
 Substances dissolved in solution.
 A solid and either a gaseous substance or a substance in solution.
For a chemical reaction to occur, the fundamental particles (atoms, molecules,
or ions) of the reactants must come into contact or collide. However, not all
collisions lead to a reaction.
 Reaction Rate
 The rate of a reaction is the speed at which the reaction takes place. Reaction
rates vary widely depending on the:
 Properties of the reactants.
 Environment in which the reaction is taking place.
  Purpose of Catalyst
Catalysts function to increase the reaction rate and effectiveness between
reactants. They accomplish this through one of two mechanisms:
 Catalysts work to bring molecules together, thereby increasing the number and
nature of collisions.
 Catalysts react with one of the reactants creating an intermediate compound
that reacts with the other reactant to form the desired product.
 A catalyst is a substance that changes the speed of a chemical reaction without
undergoing a permanent chemical change in the process. Catalyst
characteristics determine its effectiveness for driving a particular reaction to get
a desired product
Increasing Reaction Rate
 Reaction Rate Factors
• Concentration or Partial Pressure

• Surface Area

• Temperature

• Catalyst

 Not all substances will react

 Use of a catalyst is a tradeoff given safety, environmental and economic
drivers
Concentration or Partial Pressure
Concentration (Liquid System)
 As discussed before, reactants must collide in order to react. One way to
increase the reaction rate is to increase the number of collisions by increasing
the number or concentration of reactant molecules present in the container.

 Partial Pressure (Gaseous System)

 Every molecule in a system exerts a pressure on the system, which is referred
to as its partial pressure. This pressure is a reflection of the amount of energy
provided by that molecule. As discussed before, reaction rates and reaction
effectiveness are directly related to the amount of energy in the system.
Therefore, increasing the partial pressure of the reactants increases the rate of
reaction.
Surface Area
 For reactions involving substances in different physical states (i.e., solid and
liquid, solid and gas, liquid and gas), the surface area available for reaction is
another critical factor. Since this surface area represents the area available for
collisions, increasing it directly increases the collision frequency and therefore
the reaction rate.
Temperature
 Increasing the temperature of the reactants also results in an increased reaction
rate by increasing the kinetic energy of random molecular motion of the
reacting substances. As these particles increase their speed of random motion,
they experience a greater collision frequency that speeds up the reaction.

 Increasing the temperature of the reacting substances also increases the

collision effectiveness. At higher temperatures, the fundamental particles of
reacting substances have greater kinetic energy of random motion. Therefore,
when they collide they do so with more energy, resulting in a greater proportion
of the collisions being effec­tive. Generally, increasing the temperature of the
reactants increases the reaction rate.
Catalyst
A catalyst participates in a reaction but does not become consumed by it. The
catalyst does not cause the reaction to happen but permits the reaction to occur
more rapidly at a given temperature by lowering the activation energy required
for the reaction to occur. Generally, the presence of a catalyst increases the
reaction rate.

Catalysts generally increase reaction rate by one of two mechanisms:

 The catalyst provides an active site for the reaction to take place. In this
instance, the reactants are attracted to the catalyst itself and this attraction
brings the reactants together in a manner conducive to a reaction.
 The catalyst physically reacts with one of the reactants to make it either more
reactive itself or to create an intermediate compound that will then react with
the other reactant(s).
Characteristics of a Catalyst
Functional Characteristics

 High and stable activity

 High and stable selectivity
 Controlled surface area and porosity
 Good resistance to degradation
 Good resistance to high temperatures and temperature fluctuations
 High mechanical strength
 No uncontrollable hazards
 Physical Characteristics
 Supported or unsupported
 Shape of the catalyst pellets
 Size of the catalyst pellets

Supported or Unsupported
• Catalyst support is a key consideration in determining the physical
characteristics of the catalyst. To ensure proper support, catalysts must be
properly loaded into a reactor. A loading diagram is created for all
catalyst change-outs and installations
Shapes
There are several different types of shapes used for a catalyst:
 Pellet

 Ring

 Extrudate
 Monolith

 Fragment

 Sphere
Size
 The size of the catalyst is dependent upon the required contact area. For a
given shape, the size influences only the flow and diffusion phenomena. Small
pellets are often much easier to prepare and provide more surface contact area.
Supporter

 Catalyst supporters are porous solids with high total surface areas, which
provide high concentrations of active sites per unit weight of catalyst.
Common supports are activated aluminas, silicas, and aluminosilicates. The
total surface area created with these supporters varies with the crystalline
structure and the method of preparation. High surface areas are not always
desirable or advantageous in catalytic reactions. In certain reactions, this
characteristic may result in unfavorable product distribution or faster
degradation.
Active Catalyst Agent

 The active catalytic agent is responsible for the catalytic function and includes
metals, semiconductors, and insulators. For catalysts that require support, the
active catalyst agent is deposited on the catalyst by spraying or soaking.
Promoter
 Promoters are compounds that are added to enhance the physical or chemical
functions of the catalysts. An example of a promoter is chloride, which is used
in the isomerization and reforming reactions. The chemical promoter adds to
the activity of the catalyst agent, but certain promoters may also be added to
hinder undesirable side reactions.
 Heterogeneous catalysts
• A heterogeneous catalyst exists in a phase different from the reactant
molecules and is often composed of finely divided metals. For example, a
finely divided metal oxide might catalyze a reaction between molecules in the
gas phase. Heterogeneous catalysts are also known in the industry as metallic
catalysts.

Homogeneous catalysts
• A catalyst that is present in the same phase as the components of a chemical
reaction is a homogeneous catalyst. The ions in the catalyst break apart, join
hydrocarbons, and then complete the reaction. Like heterogeneous reactions,
the catalyst remains chemically unchanged
Known as a acid catalyst eg sulphuric acid
Heterogeneous catalysts
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Claus Sulfur unit
A cobalt/molybdenum catalyst is typically used and has a high activity toward:
 Conversion of H2S to sulfur.
 Reconversion of carbonyl sulfide to carbon oxides.
 Reconversion of carbon disulfide to sulfurs.
Hydrodesulfurization unit
 The catalysts used are the dual metals of cobalt and molybdenum (cobalt-
moly). Cobalt promotes the disassociation of the sulfur atom from the sulfur
compound while molybdenum promotes the hydrogenation of the radicals
Hydrotreating Process
 The catalyst used in the HDT process is nickel deposited on a silica or alumina
base. The base material helps promote the breaking apart of the unsaturated
molecules while the nickel promotes the hydrogenation reaction. The nickel
also helps promote the formation of paraffins and iso-paraffins during the
hydrogenation process.
Isomerization unit
 The catalyst used in both units is platinum in an HCl gas atmosphere. This
combination promotes the breaking apart of normal paraffins and causes them
to rejoin as an isomer with little lost as light ends. The process requires
hydrogen in the reactor to assure the complete bonding of the isomer and
prevent coking of the catalyst.

 The acid gas is generated in the process by reacting carbon tetrachloride with
hydrogen to produce HCl gas and a small amount of methane. The reactor
must be absolutely moisture-free to prevent the formation of HCl acid, which
leaches from the catalyst sites and is also highly corrosive
Naphtha reforming process
 The catalysts used for catalytic reforming are the dual metals of platinum and
rhenium. Platinum is used to change the C6 through C8 naphthenes into
benzene, toluene, and xylenes. Rhenium is used to convert the heavier
naphthenes in the charge into heavy aromatics and to prevent them from
joining into even heavier hydrocarbons
Fluidized catalytic cracking
Cracking catalyst is a manufactured zeolite (~41% aluminum oxide, ~1.5% rare
earth oxides and ~58% silica) deposited on a silica or alumina base. The FCCU
catalyst:
 Provides surface area for the cracking reaction that speeds up the reaction.
 Controls the types of products produced.
It is important to understand what can limit the effectiveness of a catalyst so the
unit or plant can be operated at it’s maximum potential. The usefulness of a
catalyst can be diminished by degradation which changes the selectivity,
increases the rate of undesirable side reactions, blocks the pores, covers the
active sites and changes the structure.
Catalyst degradation
1. Describe catalyst poisoning.
 
2. Describe catalyst fouling.
 
3. Describe catalyst sintering.
Catalyst poisoning
In process units, catalysts pick up stray metals that enter with the feedstock.
These metals are catalyst poisons and become catalysts themselves, promoting
unwanted and counter­productive reactions. They often increase the amount of
hydrogen and coke formed in the reaction. Examples of metal poisons are:
 Vanadium
 Arsenic
 Iron
 Nickel
 Copper
FCCU
 A high level of metals in the feed to the FCCU is a result of crude unit
operation and the severity on the cat feed hydrotreater. When metals in the gas
oil on the crude unit increases, the hydrotreater must increase severity in order
to reduce the metals in the feed to the FCCU. The hydrotreater cannot typically
eliminate all metals in the feed to the FCCU. The metals in the gas oil streams
are measured in the laboratory and monitored regularly by operations with the
diluted color measurement
Reforming Unit
 A permanent catalyst poison for the reformer is metals. Again, these typically
all come into the process with the feed

Isomerization Unit
 Metals, sulfur, nitrogen, and water are permanent catalyst poisons in the
Isomerization Unit. The metals, sulfur, and nitrogen block the active sites on
the catalyst and prevent reaction. These cannot be removed from the catalyst.
 Excessive water strips chlorides from the catalyst and cannot be replenished
with time. The chloride on the catalyst is critical to the operation of the
Isomerization Unit.
Fouling
 Catalytic activity may be lost due to the formation of carbon or due to the
deposition of impurities or dust in the catalyst. Coke and heavy hydrocarbons
can foul a catalyst by plugging pores or covering active sites. The formation of
carbon is reversible in some cases. The catalyst can be taken off stream and the
carbon removed by oxidation
 Fouling can also occur due to impurities in the reactant gas. These impurities
react with the catalyst and reduce the catalyst’s activity. Fortunately, the
reaction between the catalyst and the impurity is often very strong and the
impurity is completely adsorbed in the first few percent of the catalyst bed.
Because of this, the catalyst bed is generally designed to be a little larger than
necessary

 Nitrogen carryover to the unit is a result of a major unit upset and is difficult to
remove. Nitrogen poses a lesser threat to catalyst activity than sulfur, but is a
more accurate way of monitoring the deactivation of the hydrotreating catalyst
Sintering
 Sintering occurs in high temperature operations. High temperatures, such as
those caused in a temperature runaway, fuse together the passageways or
openings in the catalyst. Sintering closes the catalyst pores and vaporizes the
catalytic metal off of the ceramic bead

There are two distinct mechanisms for sintering:

 The crystallites may continuously emit and collect atoms. Since the atoms will
be more stable at the surface of a large particle than that of a small particle, the
atoms will typically migrate to the larger particle.
 The particles may move on the surface. When the particles come into contact,
they may merge into a single, larger particle
 High temperature in the process will cause catalyst sintering. This can occur
during a regeneration cycle for the FCC catalyst and Reforming catalyst.
During the regeneration of catalyst, oxygen is injected into the process to burn
off heavy carbon from the catalyst. This process is tightly controlled and must
be monitored closely. If too much oxygen is sent through the regeneration
cycle, excessive temperatures can be reached very quickly.