Mass and Energy Balances

There is no theory part for this section, as it is relatively self-explanatory. This aspect of chemical
engineering needs one to understand the concepts of balances and basic problem solving skills. In all,
mass and/or energy cannot be created or destroyed. It can change forms, but it always has to go
somewhere. Therefore, all components must be fully accounted for.
+ = +
Problems 1-4 are all based on the following information. Aspirin is made in an aquesous reaction
between salicylic adic and acetic anhydride according to the following reaction
27 6 3 () + 4 6 3 () 29 8 4 () + 2 ()
Feed streams of 27.2 kg/hr and salicylic acid in 74.7 kg/hr water and 15.1 kg/hr acetic anhydride join
with a recycle stream before entering the reactor. Reaction proceeds to 50% conversion of the acetic
anhydride. The stream exiting the reactor passes through a separator that yields a product stream
containing 34.9 kg/hr aspirin and a recycle stream with 0 aspirin. The recycle stream contains equal
moles of salicylic acid and acetic anhydride, and it circulates water at 18.0 kg/hr.

Because there is a chemical reaction, with 50% conversion, a mass balance does not sufficiently describe
the system.
Feed:
= 27,200

= 197.1
138

= 15,100

= 148.039
102

 = 74,700
Product:
= 34,900
Recycle Stream:
= 18,000

= 4,150
18

= 193.89
180

= 1,000
18

Applying a mole balance to Salicylic acid

() +
197
( ) + 0( ) = 194

There are 194 mols/hr reacted because there is a 1:1 ratio between salicylic acid and the product
aspirin, which is fully described in its output.
= 3

Now Acetic anhydride

194
( ) + 0 ( ) =
() +
148

2
There are 194/2 mols/hr because there is a 1:2 ratio between acetic anhydride and the product aspirin.
= 51
Water balance
4,150

194
( ) +
( ) = 0 ( ) +

Here the water is a product where 1 mol of water is created for every 2 mols of aspirin produced.

A mole blance can done around the separator for just the water component at this point
= 4,247

3 = 1,000

+ 4,247
= 5,247

The next step to fully define the process is a mol balance around just the separator. This is the same
concept, where the mols that enter must also leave in equal amounts.
Aspirin Balance around Separator:
= 0 ( ) + 194

( )

Remembering that there is a 50% conversion of acetic anhydride and twice as much aspirin created for
what did react.
= 194

1
0.5 2 . = 3
2
Therefore, there is an equal amount of mols of acetic anhydride that enter the reactor, in relation to the
amount of aspirin that exits the reactor.

2 = 194

Since 50% of it was converted through the reactor

1

3 = 2 = 97
3

Applying a balance of acetic anhydride around the separator finally

( ) = 51
( ) + 4 ( )
97

( )

Now the problem is starting to come together. There is an equal amount of mols of acetic anhydride and
salicylic acid in the recycle stream. Therefore,
4 = 46

4 = 46

A mole balance around the separator is can now be defined for salicylic acid
3

3 = 4 + 5 = 46
+
= 49

Now only mole balances need to be applied to mixing point B

Salicylic Acid:
2 = 1 + 4 = 197
Water:
2 = 4,150

1)
A)
B)
C)
D)

+ 46
= 243

+ 1,000
= 5,150

The flow rate from the reactor to the separator is most nearly.
117 kg/hr
146 kg/hr
223 kg/hr
340 kg/hr

This is from 2 to 3 on the block diagram above.

Separating Components
Salicylic Acid

49
138
= 6,762

Acetic anhydride
97
Water

102
= 4,998

5,247
Salicylic Acid

18

= 94,446

49

138
= 6,762

194

180
= 34,290

Aspirin

Summing up the previous components and converting to kilograms yields

= 141

2)
A)
B)
C)
D)

The recycle ratio is most nearly:

0.154
0.199
0.248
0.371

Recycle ratio is the mass flow of the recycle stream divided by the product stream.
First add up the mass flow of the product stream:
Acetic Anhydride
51
Water

102
= 5,202

4,247
Aspirin
34,290
Salicylic acid
Summing up

18 = 76,446

(100% )

138
= 414

5 = 116.4

Now the same thing must be done for the recycle stream.
Water
18
Acetic anhydride

( )

46

Salicylic Acid
46
Summing Yields

102 = 4,692

138
= 6,348

4 = 29.04

Therefore Recycle Ratio is

= 0.249
=

116.3

Note: Due to the large amount of converting, adding and rounding, small amounts of numerical error
may come up in these problems.
29.04

3)
A)
B)
C)
D)

The composition of the recycle stream is most nearly.

18.1 wt% salicylic acid, 18.1% wt% acetic anhydride, and 63.8 wt% water
21.9 wt% salicylic acid, 16.2% wt% acetic anhydride, and 62.1 wt% water
23.2 wt% salicylic acid, 12.9% wt% acetic anhydride, and 63.8 wt% water
53.5 wt% salicylic acid, 39.5% wt% acetic anhydride, and 6.98 wt% water

This problem is simple because we have already defined the recycle stream fully. The only thing we need
to do is be sure to use mass flow rates because it is defined in terms of weight percent.
Water

Salicylic Acid

18

= 0.619 = 62%
29.04

= 0.219 = 21.9%

29.04

6.348

Acetic Anhydride

= 0.162 = 16.2%

29.04

4.692

4)
A)
B)
C)
D)

The conversion of salicylic acid in the reactor is most nearly

20.2%
50%
79.8%
98.5%

Because this is dealing with a chemical reaction, the conversion must be in terms of mols and not mass.
From the above information

49

49
=
= 20.2%
242
The book says conversion is the amount remaining divided by the total moles, but I disagree with that
definition. Hence, the books answer would be 79.8%.
242

Problems 5 and 6 are based in the following information

A tank contains 23.7 wt% NaOH in water. After adding 45.1 kg of NaOH pellets, the solution is now 34.2
wt% caustic.
5)
A)
B)
C)
D)

The original mass of the solution is most nearly

102 kg
283 kg
350 kg
385 kg

This problem can be solved with a NaOH component mass balance.

NaOH original mass%*original wt + what was added = new NaOH mas%*(original weight+mass added)
0.237 + 45.1 = 0.342( + 45.1)
0.105 = 29.6785
= 282.63

6) The heat of solution for sodium hydroxide in water is -42.6 kJ/mol. The heat change after adding
the pellets is most nearly
A)
B)
C)
D)

48 MJ generated
48 MJ absorbed
120 MJ generated
120 MJ absorbed

Since 45.1 kg NaOH were added

45,100

42.6
= 48,035
39.997

It is generated, because the sign is in regards to the system. The system loses 48 MJ of energy,
therefore it is generated by the person who is doing the process.
7) 0.250m3 of water at 20oC is heated up to 100oC by injecting saturated steam at 100oC. Calculate
the amount of steam needed if heat losses total 3,750 kJ.
A) 1.67kg
B) 8.86 kg
C) 10.5 kg
D) 38.7 kg
This is a relatively simple energy balance, but you need to look up the enthalpy value of saturated steam
at 100oC

= 2,257

= +

4.184
80

3

2,257

3,750 + 0.250 3 1,000

=

= 38.7

Two evaporators, A and B, are used to concentrate a 50% aqueous KCl solution to a 90% aqueous KCl
solution. The feed stream 1 has a flow rate of 1,000 kg/hr

8) If the flow rate of steam 2 is twice the flow rate of stream 4, what is most nearly the flow rate
of stream 4?
A) 135 kg/hr
B) 146 kg/hr
C) 148 kg/hr
D) 153 kg/hr
Following conservation of mass

Also

1,000
= 2 + 4 + 5

2 = 24
1,000

= 34 + 5

This problem is also a little bit ambiguous, the first concept that one must understand is that none of the
KCl evaporates through streams two and four, since KCl is nonvolatile. So since Feed 1 has 50% water
and 50% KCl, there are 500 kg/hr flowing in each.
Now that we know that all the KCl flows into stream 3 and then into stream five, We know that stream 5
also has 500 kg/hr of KCl. And the problem statement tells us that there is 90% KCl in the stream 5.

= 555.56
5 =
0.90

The problem now is ready to be solved.

500

1,000

= 34 + 555.56

4 = 148.15

9) What is most nearly the concentration of KCl in stream 3 if the flow rate of stream 4 if the flow
rate of stream 4 is 200 kg/hr?
A) 66%
B) 71%
C) 76%
D) 80%
From the above problem, we already know that

4 = 200

A mass balance around the second evaporator says

5 = 555.56

3 = 5 + 3 = 755.56

Because there are 500 kg/hr of KCl in feed 5, that is the amount in stream 3 also
4 =

500
= 0.661
755.56

Thermodynamics:
Thermodynamics is a branch of science that lends substance to the principles of energy transformation
in macroscopic systems
Postulate 1: There exists a form of energy, known as internal energy, which for systems at internal
equilibrium is an intrinsic property of the system, functionally related to the measurable coordinates
that characterize the system.
The First law of thermodynamics: The total energy of any system and its surroundings is conserved
Heat is energy crossing the system boundary under the influence of a temperature difference or
gradient. Heat, Q, is positive when energy enters the system and is negative when heat leaves the
system.
Work again is energy in transit between a system and its surroundings, but results from displacement of
external force acting on the system. W is positive when work is done on the system and is negative
when work is done by the system.
Only applying to closed systems:

= +
= +
A key thing to remember is that heat and work are not state functions. They are not properties of the
system or functions that characterize the system.

Postulate 3: There exists a property called entropy, which systems at internal equilibrium is an intrinsic
property of the system, and is related to the measurable coordinates that characterize the system.

where St is the total entropy and T is the absolute temperature.

Second Law of thermodynamics: The entropy chance of any system and its surroundings; considered
together, resulting from any real process is positive, approaching zero when the process approaches
reversibility.
The second law essentially requires that the entropy of an isolated system either increases or will
remain constant when the system reaches equilibrium
Postulate 5: The macroscopic properties of homogeneous PVT systems at internal equilibrium can be
expressed as functions of temperature pressure and composition only. If you have two of the three, you
can fully describe the system.

Consider the steam power plant shown. Assume that the condenser and boilers pressures are constant
and that the turbines operate reversibly and adiabatically. Neglect any enthalpy change through the
pump. Make-up water is added at the same temperature as the saturated liquid condensate.

1)
a)
b)
c)
d)

What is the total power developed by both turbines?

140kW
280kW
470kW
990kW

First of all, one must find the flow rates into the turbines before doing anything else. The flow into
turbine one is easy.

1 = 11,500

The flow into turbine two is the m1 minus what leaves at part D

2 = 11,500
4,500
= 7,000

The steam that leaves turbine 1 is at 300oC and 600 kPa, its entropy and enthalpy values can be found
using the steam tables.

= 3061.6
= 7.3724

The steam that enters turbine 1 is at the same entropy level as when it exits. This is because the process
is reversible. However, this time the pressure is at 1000 kPa. Because two state functions are known, hc
and TC can be found from the tables, but interpolation is required.

 = 3,203.9

= 371.74

For turbine 2 steam enters at 350oC the pressure is 600 kPa. The pressure does not increase because the
reboiler operates at constant pressure. Find the entropy and enthalpy values from the table

= 3,165.7
= 7.5464

The steam now leaves at the same entropy, but now at 200 kPa

= 210 = 2891

The energy gained by the turbines is an energy balance of the change in enthalpies.
= 1 (1 1 ) + 2 (2 2 )

= 11,500 (3,061.6
3,203.9 ) + 7,000
(2891
3,165.7 ) = 3.559106

Energy is lost by system, but is gained by the turbine. Must convert to kJ/s to obtain kW.
= 989
2)
a)
b)
c)
d)

Calculate the heat requirement by the boiler.

1.2 MW
1.6 MW
8.7 MW
8.8 MW

= 1 ( ) + 2 ( )
We have all of the enthalpies except for hb. Because the condenser operates at constant pressure it is
saturated liquid at 200 kPa.

= 504.69

= 11,500 (3,203.9
504.69 ) + 7,000
(3,165.7
3061.6 )

= 3.167107
= 8,825

3) The powerplant efficiency is most nearly

a) 5.5%
b) 11%
c) 14%
d) 40%
=

989
=
= 0.112 = 11%
8,825

4) Calculate the efficiency of a Carnot cycle operating between the boiler and condenser saturation
temperatures.
a) 8.0%
b) 37%
c) 39%
d) 73%
It is already known that the TH is 371.74oC. Tc is 120.2oC from the steam tables of 200 kPa saturated
liquid just after the condenser.

=

It is extremely important to remember that this must be in Kelvin and not degrees Celsius!!!!!!
(371.74 120.2)
=
= 0.39 = 39%
(371.74 + 273)
Problems 5 and 6 are based on the following information.
Air at 22.0oC and 50% relative humidity passes through a cooling tower at a rate of 2,500 m3/min. The
saturated air exits the tower at 31.0oC. Water enters the tower at 35.0oC. and 3,250 kg/min.
Water exits the tower at a temperature of
A)
B)
C)
D)

21.4oC
22.0oC
23.1oC
26.0oC

Here one would assume that the heat lost by the water equals the heat gained by the air.
= ( ) = ( )

(35 )
= 3,250
4.18

= 2,500
1
(105.5
43.1
)
3

0.847


= 21.40

Mass Transfer
Mass transfer deals with diffusivity and mass transfer coefficients. It also deals with common flux
equations, and material balances are involved in typical systems. The basis of mass transfer is that it is
driven through a concentration difference. Water evaporates because the concentration of liquid water
is greater than the water concentration in the air.
Ficks First Law- This law relates flux of a component to its composition gradient, employing a constant
of proportionality called diffusivity. It can be written in several forms.

= ~~

JA is the molar flux with respect to volume average

Middle is Molar flux with respect to molar average velocity
=

= + =
=1

+ =1

+ =

=1

The summation aspect accounts for conveyance (heat transfer equivalent of convection), which is the
amount of component A carried by the net flow in the direction of diffusion. Its impact on the total flux
can be as much as 10%, but in most cases, it is able to be ignored.
Mass Diffusivity, DAB, is the diffusivity constant in m2/s. It relates the flux to the concentration gradient.
Mass transfer requires information about the bulk motion of the medium in which diffusion occurs.
Self-Diffusivity is denoted by DAA, is the measure of mobility of a species within itself. Not normally
studied in chemical engineering. Typical case is a radio active isotope.
Mass Transfer Coefficient- Denoted by kc, kx, Kx. These represent rates of transfer that are greater than
diffusion alone, as a result of convection or turbulence that occurs at the interface where mass transfer
occurs.
Fundamental Mass Balance
= +
Material Balances- Whenever mass transfer applications require equipment of specific dimensions, the
flux equation is not enough to fully describe it. If given simple geometry, a macroscopic balance can
suffice.

=1

=1

= +

M represents the mass in the unit volume at any time

mi is mass flow rate through port kg/s
ni is mass flux through port (kg/m2)
Acsi cross sectional area m2
Individual material balances can also be applied.

=1

=1

= + +

mij is component mass flow rate=miwij or w is mass fraction of the component

rj is reaction rate (generation or consumption per unit volume)
It can be inconvenient to measure mass flow rates, the product of density and volumetric flow rates can
be used instead

= +

= + 2 +

Flux Expressions: Simple Integrated Forms of Ficks First Law

These are simplified flux equations that can be used in one dimensional steady state problems with
binary mixtures.
Equimolar counter diffusion (NA=NB)

= =
=
( )

Unimolar diffusion (NA 0, NB=0)

1

= + =
(
)

1
Steady State Diffusion (NA NB 0)

+
= + ( + ) =
(
)

+
Important Conversion between Partial Pressures and Concentrations

= (2 1 ) =
( 1 )
2
The last part is impossible to solve unless the ratio of the fluxes is known. It is impossible to solve two
equations and two unknowns because they are dependent on eachother.
Diffusivity Estimation-Gases
If possible, experimental values of diffusivities are much more accurate than empirical or semitheoretical equations. There are numerous relations between diffusivity and variables that affect it. It
should be known that diffusivity is increases with increasing temperature, molar mass, and decreases
with increasing pressure and viscosity.
Diffusivity Estimation-Liquids

Diffusivity can be correlated much easier than gases because its density is generally constant with
changing pressure and temperature. Increasing temperature does increase diffusivity, and increasing
electrolyte charges and viscosity will decrease DAB.
Diffusion of Fluids In Porous Solids
Diffusion in porous solids is the most important factor in common processes such as adsorption, ion
exchange, drying, heterogeneous catalysis, and leaching. It is similar to bulk diffusion only tortuosity()
that expresses hindrance by the pore walls. The Deff can be calculated from the DAB given and its other
values.
A few correlations of this are shown below
Bulk diffusion
=
Knudsen Diffusion

0.5
= 48.5 ( )

( )
=

The problem would now be solved with the adjusted DAB in m2/s
Interphase Mass Transfer
When material transfers from one phase to another, there is resistance in each phase to the
concentration gradient.
= ( ) = ( )
pi is partial pressure of solute at intercace
p is partial pressure in bulk gas
kg is gas phase mass transfer coefficient
kl is liquid phase mass transfer coefficient

In dilute solutions it can be expressed as

= ( ) = ( )
xi mole fraction solute in liquid at interface
yi mole fraction solute in gas at interface
y mole fraction in bulk gas
yi mole fraction solute in gas at interface
Mass-Transfer Principles: Concentrated Systems
This case is when concentrations in the gas and or liquid phase are large; the equations for dilute
systems are no longer applicable.
=
where NB=0

( ) ( ) ( ) ( )
=
=
=

(1 ) (1 )
(1 )
ln[ 1 ]

(1 ) (1 )
1
ln (1 )
xBM and xBMo can be calculated by substituting x for y in the above equations.

Mass Transfer Problems

Problems 1-4 air flows through a combustion chamber held at 1145K and 101.3 kPa. Oxygen diffused
through a 1.5 mm thick stagnant film of air to a flat carbon surface where it reacts instantaneously to
form carbon dioxide. No reaction occurs in the gas film. The diffusivity of oxygen in the gas film is
1.30x10-4 m2/s.
The rate of oxygen to the surface is most nearly
A) 0.176 mol/m2*s
B) 0.194 mol/m2*s
C) 0.208 mol/m2*s
D) 0.922 mol/m2*s
The first way to start this problem is defining rate of diffusion in the z-direction

=
+

=1

However, since we are dealing with gases, it is easier to solve in the form of two species with partial
pressures.
=

+ ( + )

2 + CO2
Because one mole of O2 forms one mole of CO2
2 = 2
This causes the second term in the above NA equation to cancel out.

+ (2 2 )

Now the integrals must be separated and solved separately

=

2 ,2

1 ,2

p1=0 because the reaction at the surface is instantaneous, therefore there is no oxygen present at the
carbon surface. p2 is equal to the partial pressure of oxygen in air. Air takes up 21% of all air
2 = 0.21 101.3 = 21.273
(2 1 ) =

( 2 )
1

2
1.30104
0 21,273

= 0.19366 2
3

8.3145 (
) 1145 0 1.510

2) The partial pressure of carbon dioxide 1mm from the carbon surface is most nearly
A) 7.1 kPa
B) 14 kPa
C) 21 kPa
D) 34 kPa
Because CO2 is a product, an overall mass transfer equation must first be implemented

+
+ = 0

Because it is at steady state, the second term can be eliminated, RA can also be eliminated because the
reaction does not happen in the gas film

=
=0

From problem 1 we already know

=

Therefore
2
= ( ) ( 2 ) = 0

Since Dm/RT 0 we know;

Two simple integration yields

2
=0
2
= 1 + 2

Boundary Conditions are needed to solve this equation:

At z=0 mm
2 = 21.3
At z=1.5 mm
2 = 0

Now we have defined the equation

21.3 = 0 + 2
2 = 21.3
0 = 1 (1.5) + 21.3

1 = 14.2

2 = 21.3 14.2

1 = 7.1

3) The mass-transfer coefficient for oxygen in the gas film is most nearly
A) 1.30x10-4 m2/s
B) 1.38x10-3 mol/m*s
C) 8.67x10-2 m/s
D) 0.922 mol/m2*s
This problem can be solved immediately if one knows that almost all mass-transfer coefficients have the
units of m/s. However, we will solve this problem as if one did not know that in case the exam has
correct units for all problems.
The basic mass transfer coefficient is
= (2 1 )
=
Subbing out NA

( 1 )
2

2 1

=
( 1 )
(2 1 ) 2

Rearranging

2
4
1.3010

= 0.08667
=
=
3
2 1
1.510

4) If the oxygen reacts instantaneously with the carbon surface to form carbon monoxide instead of
carbon dioxide (all other parameters remaining unchanged), the rate of oxygen diffusion to the surface
is most nearly
A) 0.176 mol/m2*s
B) 0.194 mol/m2*s
C) 0.208 mol/m2*s
D) 0.922 mol/m2*s
The main difference in this problem is now the reaction has changed.
1
+ CO
2 2

Therefore 2 = 2
Now the NA equation can be set up as
=

( + )

( 2 )

Subbing In
Separating Variables

(1 +

)=

1 +

=1+

1
=

(2 1 ) =

1
( )

2
21.3

2

(1.30104 ) (101,300) ln (1 +
)
ln
(1
+
)
ln()
101.3
=
=
=

2 1
2 1
8.3145
1145 (1.5 103 )

= 0.17599 2

Problems 5 and 6 are based on the following information
A packed column is used to reduce the levels of a pollutant in a gas stream from a mole fraction of 0.025
to a mole fraction of 0.00015. The gas stream flows at a rate of 10.0 m3/min while pure water enters the
top of the column at a rate of 15.0 kg/min. The 2.25 m diameter tower will be packed with 19mm
ceramic Raschig rings, providing an interfacial surface area-to-volume ratio of 262 m2/m3. The overall
mass transfer coefficient based on the gas-phase driving force is 69.4 mol/m2*h. The system operates at
40oC and atmospheric pressure. The pollutant follows the Henrys law relation with the Henrys law
constant to equal 1.75x105Pa.
5) The pollutant mole fraction in the exiting water stream is most nearly
A)
B)
C)
D)

8.68x10-5
0.0116
0.0145
0.0533

This problem starts with a mole balance.

+ = +
Pure water flows in, so xin=0 in terms of the pollutant. rearranging
=

( )

This problem needs to be solved in terms of gas and liquid molar velocities, because molar fraction is
what is reduced in the problem
103 60
5
(1.01310
)
(
1

) ( )
=
=
= 5,874 2
2
3
(2.25 )

(8.314
) (313) (
)
4


=
=

60

(15 ) (60
)

= 12,575 2
2
(2.25 )

0.0180
(
)
4

Now the problem can be solved

5784 2

(0.025 0.00015) = 0.0116

= ( ) =

12,575 2

6) The total height of packing required to achieve the desired separation is most nearly?
A)
B)
C)
D)

1.61 m
5.81 m
20.3 m
53.5 m

From chemical engineering, The total height of packing required is the product of the transfer unit
length and the number of transfer units
= ()()
=

1 2
( )

Log mean driving force is

(1 1 ) (2 2 )
1
ln ( 1
)
2 2
y*2=0, because this relates to when the water entering is pollutant free, the * relates to the equilibrium
value of the water where only some pollutant may exist.
The gas stream that enters the column can be related using henrys law constant given above
( ) =

1.75105
1 = (
) (0.0116) = 0.0200

1.013105
Now the log mean driving force can be calculated
(0.025 0.02) (0.00015 0)
( ) =
= 1.38103
0.025 0.02
ln(
)
0.00015
1 =

The transfer unit height now must be calculated. This HTU is the ratio of the gas velocity to the overall
gas capacity coefficient. The coefficient is the product of the overall mass-transfer coefficient and the
interfacial surface area to volume ratio

=
=

5874
(69.4

2
)(262
)
2
3

= 0.323

 =
Total height of packing is

1 2
0.025 0.00015
=
= 18

( )
1.38103

= ()() = (0.323)(18) = 5.81

Heat Transfer

Heat Transfer by Conduction

Fouriers Law
=

Q is rate of heat transfer in Watts

k is the thermal conductivity (constant depending on material)
A is the plane area
dT/dX is the change in temperature divided by plane thickness
For a 1-Dimensional plane, with homogeneous heat transfer
(1 2 )
=

A resistance analogy can be made in heat transfer the form can be used as. The equation remains the
same, but appears different.
1 2 1 2
=
=
/

R=K/W
One Dimensional Conduction
In the absence of an energy source, Q is constant with distance
Because the area (A) is based on the medium that the heat is flowing through, the equation does change
and affect the integral.
1 2
= 2
2
ln ( ) /(2)
1
1 2
=
= 4 2
(2 1 )/(41 2 )
=

Conduction with Resistances in Series:

At steady state temperature profile, and three constant thermal conductivities and no source terms. The
rate of heat transfer through each of the layers is the same.
1 2
=

+
+

1 2
=
+ +
Additional Resistance occur if the surface of the solid is in contact with a fluid.
Newtons Law of Cooling:
= ( )


1/()
1
So essentially =

Two and Three dimensional Conduction:

This describes form in three-D, same as 1-d but now must apply three separate integrals in one
equation. Remember under steady-state conditions everything always equals zero.

( ) +
( ) + ( ) + = 0



S is the heat source that may or not be present (W/m3)
Unsteady-State Conduction:
In the case of unsteady conduction, the system that we are studying is now changing temperature with
time. The equation remains the same as above, but no longer equals zero.

=
( ) +
( ) + ( ) +



1-D Unsteady State Conduction

2
= 2

Alpha is the thermal diffusivity, which varies based on medium heat flows through

2
=

The lumped capacitance method is a shortcut method used in unsteady state conduction. It applies to
small metals with high thermal conductivities, and the temperature of the solid is assumed to be
uniform throughout.

= 1 ( 1 )

b=1, plate thickness 2R

b=2 cylinder, diameter 2R
b=3 sphere, diameter 3R
boundary conditions are as follows
for t<0 T=Ti (initial temperature)

at r=0 = 0 ( )

ar r=R = ( )

One way to test the lumped capacitance analysis is using the Biot number, but the Fourier number must
also be known.

< 0.2 ,

Solutions to the lumped capacitance method can be expressed as

= exp (
)

and

= 1 (
)

=
Heat Transfer by Convection
Newtons Law of Cooling applies to heat transfer. The rate of convective heat transfer between a surface
and a fluid is given by Newtons Law of Cooling
= ( )

= 2
= 2

If you consider a fluid with bulk temperature T, flowing in a cylindrical tube of diameter D, with constant
wall temperature Ts, an energy balance on the section is

= ( )

m is mass flow rate

x is distance from inlet
Tin is inlet temperature
L is distance downstream

()

= exp (
)

This equation applies to a section downstream from the inlet

Heat Exchangers
=
A is heat exchanger area and
( ) ( )0
ln[( ) ( )0 ]
Counter flow means that the hot and cold streams flow in opposite directions of the heat
exchanger, parallel flow means that the hot and cold streams start and end in the same spot.
=

Natural Convection
Many dimensionless quantities are used in convection, one of these is the nusselt number.

=
=

Natural convection occurs when a fluid is in contact with a solid at a different temperature.
Temperature difference drive the gradient and heat transfer, forced convection would be a fan
that forced blowing of air over a surface.

Key dimensionless parameters are the Rayleigh number

= 3 /

There are numerous ways to calculate the Nusselt number, depending on the geometry and
flow condition
Forced Convection
Forced convection heat transfer is the most common mode in the process industries. There are
also a bunch of variations of the nusselt number that can be calculated depending on whether
the flow is turbulent, laminar, internal or external.
Finned Tubes
Fins can be used to increase the surface area on the solid, this allows for faster heat transfer than if
there were no fins
0.6
0.6

= 0.4 (
)
0 0
b= 5.29 SI
VF is fluid velocity
D0 is outside diameter

0 =
0

1) Determine the overall heat-transfer coefficient, U0, based on the outer surface of a brass tube
(2.5 cm inside diameter, 3.34 cm outside diameter, and thermal conductivity of 110 W/m*K)
given the following conditions: insider and outside heat-transfer coefficients are 1,200 W/m2*K
and 2,000 W/m2*K respectively, and the fouling factors for inside and outside surfaces are 5,500
W/m2*K each.
A)
B)
C)
D)

155 W/m2*K
480 W/m2*K
564 W/m2*K
642 W/m2*K

The overall equation for this process is as follows

0
ln ( ) 0
1
1
1
=
+
+
+
+

2
0 0 0

ln ( 0 )

1
1
1
0

=
+
+
+
+
(
(0 )

2
0 0 0
)
This is because the area is the surface area pipe, so the area is pi*D*L
0
0 0 ln ( )
1
0
1
=
+
+
+ 0 +

2
0
This equation is the way the NCEES reference handbook has it. However, the units for fouling are flipped
in the above problem, so inverses of fouling factors must be put in the equation
3.34
3.34(
)
1
3.34
3.34
1
2.5 +
=
+
+

1,200 2.5 2.5 5,500

2 110
2,000 2

2
2

1
+

5,500 2

1
= 0.006436

= 155.378 2

Problems 2 and 3 are based on the following information. After a liquid product (heat capacity= 1,070
J/kg*K) is cooled from 370K to 325K, single pass heat exchanger. The production rate is 2,130 kg/hr.
Water (heat capacity 4180 J/kg*K) is supplied as coolant at 0.185 kg/s and 275K. The overall heat
transfer coefficient is 242 W/m2*K
2)
A)
B)
C)
D)

The exit temperature of the water is most nearly

290K
310K
320K
340K
= =
We have everything to calculate the heat lost by the hot stream.

= 2,130

1,070
(325 370)
3600

= 28,488.8
Since =

28,488.8 = 0.185
4,180
( 275)

= 311.84
3)
A)
B)
C)
D)

The heat transfer surface are is most nearly

1.81 m2
1.89 m2
2.18 m2
2.86 m2

This comes from the most basic heat exchanger equation

=

28,488.8 = 242 2
(2 ) ()

(0 ) ( )
=
= 54.37

ln( 0 )

28,488.8 = 242 2
54.27

2
= 2.16

4) A 1cm thick aluminum plate-and-fin heat exchanger (thermal conductivity=229 W/m*K)

provides heat-transfer between water and air. The straight rectangular fins are 2.25cm long
0.125cm thick spaced 0.8 cm apart. The air side heat transfer coefficient and fin efficiency
5.0W/m2*K and 95% respectively. On the water side they are 78.5 W/m2*K and 90%
respectively. Determine the increase in heat transfer provided by placing these fins on the bare
aluminum plate.
A) 29.7%
B) 92.5%
C) 632%
D) 662%
= +
= 0 (0 ) + f (0 )
I am not a huge fan of this problem, the problem does not give you an area of the plate, and also does
not give you the number of fins. It is rather ambiguous. In order to solve a 1m x 1m basis should be
assumed.

2
0 = 12
(1 0.00125 ) = 0.84375
0.008

1
= #
=
(2 + )
0.008

= 125 (2 1 0.0225 + 0.00125 1

= 5.782
Air and water side heat transfer rates must be calculated first

( 2 ) = 0 (0 air ) + f (0 )

2
= 0.84375 5.0 2
(0 ) + 5.78 2 5.0 2
0.95 (0 )

= 31.6738 (0 )

( 2 ) = 0 (0 ) + f (0 )

= 0.843752 78.5 2
(0 ) + 5.782 78.5 2
0.90 (0 )

= 474.591 (0 )
0 = (# )

The above values are calculated for the base with fins only. There is water, the plate and then air, so a
resistance problem can be solved to figure out the heat transfer.

=
1

1
+ +

=
= 29.6767 ( )
1
0.01
1
+
+
31.7
229
474.591
Compared to without fins where the original values are used instead of our adjusted ones.

= 4.7 ( )
1 0.01
1
+ 229 +
5
78.5

Percent Increase In heat Transfer:

29.6767
=
=
= 6.31 = 631%

4.7
Although this seems ridiculously high, over 125 fins are added to a 1m2 surface, so obviously the heat
transfer is going to increase significantly.
Problems 5 and 6 are based on the following information and graph.
A food company produces spaghetti with meatballs. The sauce, pasta and meatball components are
cooked separately before mixing and canning. Meatballs are rolled to a uniform 2.0 cm diameter and
helt at a constant 8oC before cooking. They are steam cooked in an environment where water vapor at
100oC condenses on the meatball surface with an effective film coefficient, h, of 8,500 W/m2*K. Assume
the meatballs are uniform with the following constant thermal characteristics.
thermal conductivity=0.45 W/m*K
density=750 kg/m3
heat capacity= 3.0 KJ/kg*K
The following logarithmic temperature history chart for the center of a meatball may be used when
internal temperature resistance dominates.

5) In order to neglect internal temperature resistance involved in heating a body, the biot number
must be
A) less than 0.1
B) less than 1
C) greater than 1
D) Bi is not a factor
Easy problem from heat transfer. In order to use the lumped capacitance method, the biot number must
be less than 0.1, perrys says 0.2, but regardless it must be small. This case usually applies to small
objects that have high conductivities, so it can be considered that the temperature of the object is
constant throughout.
6) To prevent botulism, the center of a meatball must reach 90oC. How much time is required for
the meatballs to cook.
A) 150 s
B) 212 s
C) 250 s
D) 298s
The first thing we have to figure out is if we can use the lumped capacitance.

4
3
8,500 2 3 (0.01)
=
=
= 62.9

0.45 4 (0.01)2
So because it is must larger than 0.1 cannot use lumped capacitance.
The graph must be used in order to solve for the abscissa

90 100
=
= 0.1086 = 0.11
0
8 100
Using the graph it can be determined
We know

= 0.30
2
=

= 0.30 2

1
= 0.30 (0.01)2 750 3 3,000

0.45

= 150

Fluid Dynamics
A fluid is a substance which undergoes continuous deformation when subjected to a shear stress. If a
fluid is bound between two plates of area A, separated by a small distance H. The bottom plate is fixed.
The application of force F to the upper plate causes it to move at a velocity U. The fluid will deform as
long as the force is applied.
Shear Stress
=

( )
2

( )

Linear Velocity Profile

Y is the position within the system you are at.

There is a no-slip condition that occurs at the bounds of fluid walls. This means that the fluid does not
move if the wall is stagnant, and moves at the velocity the wall is moving at. Once again, only at the
bounds of the pipe.
The shear rate is the velocity gradient
1
=
( )

Viscosity is the ratio of shear stress to shear flow

=


Kinematic Viscosity is the ratio of viscosity to density

=
( )

Purely Viscous Fluids

Fluids that do not undergo any reverse deformation when shear stress is removes
Newtonian Fluids
All fluids which the viscosity is independent of shear rate, and may depend only on temperature and
sometimes pressure. The Newtonian fluid is the largest class of fluid of engineering importance. Most
gases and low molecular weight liquids are Newtonian.
Newtons Law of Viscosity
= =

Velocity
The term kinematics refers to the quantitative description of fluid motion or deformation. The rate of
deformation depends on the distribution of velocity within the fluid. Velocity is a vector quantity, which
can travel in three dimensions. Steady flow is one which velocity is independent of time. Unsteady flow
varies with time.
Compressible and Incompressible Flow
An incompressible flow is one in which the density of the fluid is constant or nearly constant. Liquid
flows are generally incompressible. Compressible fluids, such as gases, may undergo incompressible
flow If pressure and/or temperature changes are small enough that density is relatively unaffected.

One-Dimensional Flow
Many flows studied in chemical engineering, such as those in pipes and channels, is treated as onedimensional flow. There is a single direction called the flow direction; velocity components
perpendicular to this direction are either zero irrelevant.
Reynolds Number
Reynolds number is used to predict between two different types of flows. IN laminar flow, there are
smooth streamlines and the fluid velocity components vary smoothly with position, with time the flow is
unsteady. It appears as parabolic, with the maximum speed in the middle of the pipe. In turbulent flow,
there are no smooth streamlines, and the velocity shows chaotic fluctuations in time and space.
Velocities in turbulent flow are reported as the sum of the time-averaged velocity and velocity
fluctuation from the average.

L is the characteristic length (diameter of pipe, diagonal in rectangular)

U is velocity
p is density
mu is the viscosity
Below a critical value of Re, the flow is laminar. There is a threshold called transitional flow, and above a
new critical value the flow is now turbulent. The corresponding numbers depend on the geometry of the
system.
Conservation Equations
Three postulates, regarded as laws of physics, are fundamental in fluid mechanics. These are
conservation of mass, conservation of momentum, and conservation of energy. In addition, two other
postulates, conservation of angular momentum and the entropy inequality(see second law of
thermodynamics) have occasional use. These balances can be applied to material systems or to control
volumes in space. Most often, control volumes are used.
Macroscopic Equations
An arbitrary control volume of finite size Va, is bounded by a surface of area Aa with an outwardly
directed unit vector n. The control volume is not necessarily fixed in space. Its boundary moves with
velocity w. Fluid velocity is v.
Mass Balance
A mass balance is applied to the control volume.

+ ( )

This can be applied to special cases where the area increases or decreases at the inlet and outlet. A
simple balance shows. V is velocity (m/s) A is area (m2/s)
1 1 = 2 2
The average velocity across a surface area that is changing is
1
=

Volumetric Flow Rate
3
= ( )

Mass Velocity

= ( )

For steady flows through fixed control volumes with multiple inlets and outlets, conservation of mass
requires that the sum of inlet flow rates equals the sum of outlet mass flow rates.
Momentum Balance
Since momentum is a vector quantity, the momentum balance is a vector equation. Where gravity is the
only body force acting on the fluid, the linear momentum principle applied to the arbitrary control
volume.

+ ( ) = +

g is the gravity vector

tn is the force per unit area exerted by the surroundings on the fluid.
With the inlet and outlet velocity vectors as V1 and V2 the momentum equation becomes
(2 2 1 1 ) = 1 1 + +
M is total mass of fluid in the control volume
is a factor that arises from averaging the velocity across the area of inlet to outlet
F is force exerted on the fluid
tn is stress vector, that is normal to inlet and outlet surfaces
p is pressure
Total Energy Balance
The total energy balance arises from the first law of thermodynamics. Applied to the arbitrary control
volume, it leads to an equation for the rate of change of the sum of internal, kinetic and gravitational
potential energy. u is internal energy per unit mass, v is magnitude of velocity vector v, z is elevation, g is
the gravitational acceleration, and q is the heat flux vector.

2
2
( +
+ ) + ( + + ) ( ) = ( ) ( )

2
2

If the equivalent pressure + is equivalent across the entrance and exit then it reduces to
1 12
2 22
1 +
+ 1 = 2 +
+ 2 + +
2
2
h is enthalpy per unit mass
Ws is work of the shaft per unit mass
Q is heat input per unit mass
Is the ratio of cross-sectional area of the cube of velocity to the cube of average velocity
Mechanical Energy Balance
A balance for the sum of kinetic and potential energy may be obtained from the momentum balance by
forming the scalar product with the velocity vector.

2
2
( + ) + ( + ) ( ) = + ( ) dV

2
2

The last term is the rate of viscous energy dissipation to internal energy, also referred to the rate of
viscous losses.
= dV

Under the same equivalent pressure conditions, the mechanical energy equation reduces to
2
1 12
2 22

+ 1 + =
+ 2 +
+
2
2
1
Here lv is the energy dissipation per unit mass

Engineering Bernoulli Equation

1 1 12
2 2 22
+
+ 1 + = +
+ 2 +

2
It can also be written for incompressible, inviscid flow along a streamline, where no shaft work is done
1 12
2 22
+
+ 1 = +
+ 2

2
Friction Factor
For a Newtonian fluid in a smooth pipe fanning friction factor is calculated as such

=
2 2

This affects the shear stress as

2
=
2
Flow through Orifices
An orifice is commonly found in flow restricting devices, where in the middle of the pipe, the crosssectional area decreases and then increases to its original value.
= 0 0 = 0 0

P1 is the inlet pressure

P2 is pressure at the orifice
A0 is the smaller area at the orifice
P3 is the outlet pressure

2(1 2 )

2
(1 ( 0 ) )

= 0 0

2(1 3 )

2
(1 0 ) (1 ( 0 ) )

Fluid Dynamics
1) The flow rate of benzene is being measured by a venture meter in a pipe with a 75 mm internal
diameter. The venture meter has a throat diameter of 50 mm. A mercury manometer shows a
differential of 15 mm. The venture meter has a flow coefficient of 0.98. Under flowing
conditions, benzene has a density of 820 kg/m3 and a viscosity of 1 cP. What is most nearly the
flow rate of benzene in the pipe?
A) 0.0050 m3/h
B) 0.28 m3/h
C) 17 m3/h
D) 74 m3/h
Flow rate is what we are looking to study.

( ) = ( ) (2 )

The velocity of benzene at the throat is

=

4
1 ( )

Differential Head, is defined as

= (
1)

The SGmercury is 13.6, SGbenzene is 0.820

13.6
= 15 (
1) = 233.78 = 0.234
0.82
Now the velocity can be solved for
2
2 (9.81 ) (0.234)

= 0.98
= 2.34
4

50
1(
)
75
Now solving for the flow rate
2
0.052
3 3600
3
= 2.34 (

= 16.54
) (2 ) = 2.34 (
) = 0.004595

4
4

Problems 2-6 are based on the following information

Gasoline is being pumped through a pipe with a 150 mm internal diameter at a rate of 150 m3/h. The
pipe has five long (LR) elbows, two 45o elbows, and two gate valves. The gasoline has a specific gravity of
0.67 and a viscosity of 0.80 cP. The friction factor can be estimated from the following equation.
2
= (1.8 log ( ))
7
2) What is most nearly the velocity in the pipe?
A) 0.60 m/s
B) 2.4 m/s
C) 5.8 m/s
D) 10 m/s

Velocity in the pipe is determined as

Area can be calculated as

3
( )
=
(2 )
3
150
1
3
=

= 0.041667

3600

2
0.15
=
= 0.017671 2
4
4
3
0.041667

= =
= 2.36
2
0.017671

3)
A)
B)
C)
D)

What is the Reynolds number for this flow scheme, if the velocity is 4.1 m/s?
1.5x103
1.5 x104
2.5x105
5.2x105

Reynolds Number through a pipe is defined as

3
(0.67 10 3 ) (4.1 ) (0.15)
=
=
= 515,063 = 5.2105
1(. )

0.0080 10
4) What is the friction factor for this flow scheme if the Reynolds number can be taken as 2x104?
A) 0.003
B) 0.010
C) 0.025
D) 0.032
From the given equation in the problem statement
2
2
2104
= (1.8 log ( )) = (1.8 log (
)) = 0.0258
7
7

The length-to-diameter ratio, L/D, values for the pipe fittings are as follows.

( )
= 20

( )
= 16
45

( )
= 13

5) What is the equivalent length of the pipe fittings?
A) 8.8m
B) 24m
C) 31m
D) 35m
The equivalent length of each fitting is determined from

The diameter is 0.150 meters

= 0.150 20 = 3
45 = 0.150 16 = 2.4
= 0.15 13 = 1.95
From the problem statement we have 5 LR elbows, 2 45o elbows, and 2 gate valves.
= 5 3 + 2 2.4 + 2 1.95 = 23.7
6) What is the pressure drop through this section of pipe, if the friction factor is 0.018, the velocity
is 3.0 m/s, and the equivalent length of pipe and fittings is 650m?
A) 15m
B) 20m
C) 25m
D) 36m
Head loss due to flow is defined as
2 0.018(650)
=
=
2
0.150

2
(3 )
= 35.7798
2
2 9.81

Calculator Functions
trigonometric functions
inverse trig functions
hyperbolic functions
pi
square root and x2
extracting roots of quadratic and higher order equations
converting between polar and rectangular vectors
finding standard deviations and variances
calculating determinants of 3x3 matrices
linear regression
economic analysis and other financial functions
Strategies for the Exam
Prepare for all subjects
Maintain alertness for eight hours
Use SI units
use rms values for electrical calculations
four sig figs max
Five minutes before the end, guess on all problems
Morning section; 2 minutes per problem
FE Handbook (Table of Contents- Page 5)

Chemical Reaction Engineering (Section 7 in Perrys)

Stoichiometry balances reactions:
2 + 2 2HBr

or

1
1
2 + 2 HBr
2
2

Reactions can be balanced more than one way. In certain cases several reactions can become a network
of reactions and break down into several single-step reactions. The network represents the true
mechanism of reaction from initial reactants to products, including intermediates. Intermediates can be
molecules, ions, free radicals, transition state complexes, and other molecules.
Reaction Rate: The specific rate of consumption or production or any species i, ri, is the rate of change
of number of molecules of species i with time per unit volume or reaction medium
1
(

Rate is negative when representing a reactant, positive when representing a product.
=

Classifications of Reactions:
1) Irreversible, the reverse reaction is negligible: + C + D; only acts forward
2) Reversible: + +
3) Equilibrium: A special case with zero net rate, with forward and reverse reaction rates of a
reversible reaction being equal. All reversible reactions, if left long enough, end in equilibrium.
4) Networks of reactions: Consecutive, parallel, complex reactions.
+ C+D
Then + F + G
Reactions can also be classified by the number of molecules participating in the reaction, or number of
reactants.
1) Unimolecular: B or B + C; Only one reactant, decomposition reactions
2) Bimolecular: + C or 2 B or + C + D
3) Trimolecular: + + D or 3 D
Measuring molecularity is only useful when considering elementary reactions. Often unimolecular
reactions require a solvent, gas or energy so it is not truly unimolecular.
Other Reaction Classifications:
1) Homogeneous Gas ( methane combustion)
2) Homogenous Liquid (acid/base reactions to produce salts)
3) Heterogeneous Gas-Solid (HCN synthesis from NH3)
4) Heterogeneous Gas-Liquid (absorption of CO2 in amine solutions)
5) Heterogeneous Liquid-Liquid (liquid-liquid extraction; two immiscible phases)
6) Heterogeneous Liquid-Solid (reaction of limestone with sulfuric acid to make gypsum)
7) Heterogeneous Solid-Solid (self-propagating high temperature synthesis of inorganic pure
oxides)
8) Heterogeneous Gas-Liquid-Solid (catalytic Fischer-Tropsch synthesis of hydrocarbons from CO
and H2)
9) Heterogeneous Gas-Liquid-Liquid ( oxidations or hydrogenations with phase transfer catalysts)
Reactions can be also classified by mode of operation in the reaction system:
1)
2)
3)
4)

Isothermal constant volume (batch)

Isothermal constant pressure (continuous)
Adiabatic
Non-isothermal temperature-controlled (by cooling or heating), batch or continuous

Effect of Concentration on Rate

If given the reaction: + rC + sD

The rate is given by the empirical function: = ( ) and =

(
)

Where k is the reaction constant CA and CB are concentrations to the power of their stoichiometric
coefficient. Overall Reaction order is equal to a + b. Reaction rates can be fractional or integers. a and b
are not related to p, q, r and s. If a and b are zero, the concentration has no effect on reaction rate. If a
and b are >1 then increasing concentration increases reaction rate. If a and b are < 1 then increasing
concentration slows down reaction rate. (a and b only affect their specific concentration term)

Law of Mass Action

For elementary reactions, the law of mass action states that the rate is proportional to the
concentrations of the reactants raised to the power of their respective molecularity.

=
In this scenario, p and q determine the order, and are therefore equal to a and b.
Effect of Temperature
The Arrhenius equation relates the specific rate constant to the absolute temperature.

= 0 exp( )

Where E is activation energy, and k0 is the pre-exponential factor. Rate can vary strongly on
temperature, depending on the value of the activation energy. This equation works well or elementary
reactions, and reasonably well for global reactions over a narrow range of temperatures. A more
accurate of the Arrhenius equation is given from

= 0 exp ( ) 0 < < 1

Tm is often neglected because of the much stronger dependence on the exponential factor. When m is
larger, as it is for complex, then it cannot be ignored.
Heat of Reaction
Chemical reactions involve the evolution or absorption of energy. The enthalpy change (enthalpy of
products subtracted by the enthalpy of the reactants) is called the total heat of reaction :
= ( + + ) ( + + )
The reaction is exothermic if heat of the reaction is negative and endothermic if heat of the reaction is
positive. Magnitude of the effective heat of reaction depends on temperature and phases of the
reactants and products. Heat of reaction dependence on temperature is given as follows

() = (0 ) +
0

It is important to accurately capture the energy balance and its relation to the heat of reaction and heat
capacities. The coupling of heat reaction with reaction rate has a great effect on reactor selection and
control.
Chemical Equilibrium
If given the Equilibrium Equation:
+ cC + dD
There is a forward and reverse reaction rate:

 = =
Reaction rates depend only on reactants and their concentrations. Total reaction order =
The equilibrium constant Ke is ratio of forward divided by reverse:
=

Using the Vant Hoff Relation

( )

0 exp( ) solve

(0 )+0

it as ln () = ln (0 ) +

When the reversible reaction is not in equilibrium:

=

Conversion, Extent of Reaction, Selectivity, and Yield

Conversion of a reactant is the number of moles converted per initial or feed moles of a reactant. For
component A:

= 1
0
A limiting reactant is a reactant whose concentration at the start of the reaction is the least of all
reactants relative to the required stoichiometric amount needed for complete conversion. Once the
limiting reactant is depleted, the respective reaction stops even though other reactants are present.
Extent of Reaction relates the composition of components that participate in a reaction to each other.
0 0
=
=

0
=

Selectivity,S, of a product is the ratio of the rate of production of that product to the rate of all the
products combined. For a single product it is trivial, but with more than one product:

=
+++
Selectivity can also be solved as the rate of reaction:

= ( )

Now if given the reactions: + cC + dD

Then

+ fF + gG

Yield of a product R with respect to reactant A is ratio of rate of production of R compared to

consumption of A. Generally calculate yield with respect to the limiting reactant.

For a single reaction the yield is trivial and can be simplified as the ratio of respective coefficients.

Concentration Types
Different concentration types are useful for different reaction systems. For gas-phase reactions,
volumetric concentration or partial pressures are both useful.
Using the ideal gas thermodynamic equation of state:
=
Applying to individual components:
=
Relating concentrations to partial pressures:

For times when the ideal gas law is invalid (high pressures or non-ideal gases), a compressibility factor,
zi, can be used:

Stoichiometric Balances (7-8 may have typo)

Stoichiometric balances can be extremely useful when calculating amount of product created in terms of
the limiting reactant. If given the equation:
+ cC + dD
Here, A is the limiting reactant and XA is the conversion of A:
= 0 (1 )

= 0 (1 ) = 0 0 = 0 (0 ) = 0 0 (1 )

= 0 + (0 ) = 0 + 0 (1 )

= 0 + ( ) = 0 + 0 (1 )

The equation can be adjusted by changing moles to concentration can be done if the entire equation is
divided by the reaction volume V:

= 0 (0 )

= 0 + (0 )

= 0 + (0 )

Stoichiometric balances also apply to reaction rates:

= = =

Once again, it is best to define all concentration and mole equations in terms of the limiting reactant.
Reaction Networks

Analyzing a network for reactions is similar to independent reactions if the extent of each reaction is
known. A stoichiometric matrix is required to relate concentrations with stoichiometric coefficients.
Catalysis
A catalyst is a material that increases the rate of both the forward and reverse reactions of a reaction
step, with no consumption or generation of catalyst by the reaction. Catalysts do not affect equilibrium
composition or heat or reaction. However, it does lower the activation energy from reactants to
products. Catalytic reactions can occur at lower temperatures and faster than noncatalytic reactions.
When considering catalysis in reaction, there are three types of reactions:
1. Noncatalytic reactions, free radical gas phase reactions such as combustion
2. Homogeneous catalytic reactions with catalyst being in the same phase as the reactions and
products are in a homogeneous medium.
3. Heterogeneous catalytic reactions, involve a catalyst being a solid in contact with reactants or
products in a gas-solid, gas-liquid-solid, or a liquid-solid system. Catalyst is not uniformly
distributed. (Ex. the catalytic cracking of gasoil to gasoline and lighter hydrocarbons.

Ideal Reactors
Reactions occur in reactors. In addition to reaction kinetics, reaction rates depend on reactor type, scale,
geometry, mode of operation and operating conditions.
Material, energy, and momentum balances are essential to fully describe the performance of reactors.
Ideal reactors allow us to simplify the energy, momentum and material balances. Three types of reactors
are generally used in chemical engineering.
1. Ideal batch reactors (BRs) and Semi-batch Reactors (SBRs)
2. Ideal continuously stirred tank reactors (CSTR), including single and multiple stages
3. Plug Flow Reactor (PFR) with and without recycle

Batch Reactor (BR)

Ideal batch reactors are tanks provided with agitation for uniform composition and temperature at all
times. An ideal batch reactor can be operated under isothermal conditions (constant temperature),
temperature-programmed mode, or adiabatic mode (no heat transfer across reactor boundaries). In
adiabatic mode the temperature increases in exothermic reactions, decreases in endothermic reactions,
and constant in thermally neutral reactions.

Batch reactors can be single-phase, multiphase and catalytic or noncatalytic. Ideal batch reactors discuss
operation at isothermal conditions. This eliminates the need to consider energy. An ideal isothermal
single-phase batch reactor has the following material balance equation:

= 0 = 0

In terms of conversion:

= 0

= 0

Integrating allows to solve for batch reaction time or batch residence time, BR, required to obtain
conversion Xi, starting with Xio and ending with Xif:

BR = 0

A special case of batch reactors is constant volume or constant density operation typical of liquid-phase
reactions.

=
= 0
= 0

Residence time is:

BR =
0

Semibatch Reactor (SBR)

In semibatch operation, a gas of limited solubility or a liquid reactant may be fed in slowly as it is used
up. An ideal isothermal single-phase semibatch reactor has the following general material balance
equation:

= 0 +
= 0
= 0

Continuous Stirred Tank Reactor (CSTR)

In ideal CSTRs, composition and temperature are uniform throughout. This reactor has a continuous
feed of reactants and a continuous withdrawal of products and remaining reactants. A CSTR can operate
under transient conditions or steady state. Once again ideal CSTRs operate under isothermal conditions.
This eliminates the need for energy balance equations.
The material balance for a CSTR is as follows:

= +
= 0

At steady state then:

0
=

= 0

An apparent residence time based on feed conditions can be defined also:

CSTR =
0 = 0 0
=
0
CSTR material balance can be adjusted to:

0 ( )
0
CSTR =

IF the equation is at steady state then q=q0, and the term above can reduce to 1.
When a number of CSTRs are employed in series, the concentration profile is stepped shaped.
Plug Flow Reactor (PFR)
In a plug flow reactor all portions move with the same radially uniform velocity along parallel
streamlines and therefore have the same residence time. No mixing in the axial direction, but there is
mixing radially. As the reaction proceeds, the concentration falls off with distance. A PFR can be
operated under transient or steady state conditions. Ideal PFRs operate under isothermal conditions, to
avoid an energy balance. An isothermal single-phase steady-state PFR in which a general reaction
network takes place has the following general material balance equation:

=
= 0
= 0

In terms of conversion:

0
=

A useful equation is the required reactor volume to achieve a conversion Xi:

=
0
Apparent residence time can also be calculated for a PFR:

PFR =
= 0
0

For a Constant density system with no change in number of moles:

PFR =
0
Ideal Recycle Reactor
All reactor modes can be advantageously operated with a recycling part of the product or intermediate
streams. Heated or cooled recycled streams serve to moderate undesirable temperature gradients.
If the recycle flow rate is qR and fress feed rate is q0. Fresh feed concentration is C0 and product
concentration is C2. Composite reactor feed concentration C1 and recycle ratio are:
(0 + 2 )

1 =
=
1+
0
This adjusts the space time equations as:

This equation shows that recycling increases residence time or reactor size required to achieve the same
conversion. (1+R)>1
PFR = (1 + )

1) Type equation here.Compound A decomposes to compound R in a constant-volume isothermal

batch reactor. The concentration of A is tracked over time. Using the data provided, determine
the order of the irreversible stoichiometric equation.
Time (min)
CA (mol/L)
0
20.00
2.45
11.21
5.21
7.50
8.36
5.44
12.72
3.94
A)
B)
C)
D)

Zero
First
Second
Third

What you need to know:

Decomposition is simply R and order affects the reaction rate. Correct order will plot as linear on
graph.

= =

Zeroth order: AR
=
= 0
20
15
10

Zeroth Order

0
0

10

15

Not Linear, therefor not a zeroth order reaction

First Order: AR

1
=

0
ln ( ) =

2
1.5
1

First Order
0.5
0
0

10

15

Not linear, not a first order

Second Order: 2AR

= 2

1
2 =

1
1

=
0

0.25
0.2

Second Order

0.15
0.1
0.05

0
0

10

15

Third Order: 3AR

Linear, reaction is second order

= 3

1
3 =

1
1
2 2 =
0

0.08
0.06
0.04

Third

0.02
0
0

10

15

Not a third order reaction

2)
a)
b)
c)
d)

Under which conditions does isothermal back mixing slow conversion to product?
reaction order -1
reaction order 0
reaction order 2
Isothermal back mixing does not slow conversion

First of all, isothermal back mixing occurs in CSTR reactors, not PFRs. So we are comparing space time
between CSTRs and PFRs. The situation where > is the situation where back mixing slows
conversion.
From FE Reference Handbook:

0

=

Now the equations should be evaluated at each condition:

= 0

A) reaction order -1

= = (1

2
2

0 (1 )
0
0
2
= 0
=
(1 ) =
( )

2
0
2
0
0
=
0 (1 ) =
(1 )

Now compare space times:

=?

Here it is <1 So it does not slow in this case

B) Reaction order 0

Here: = So it still is not slower.

C) Reaction order 2

Here

>1

0
=
=

0
0
=

1
1
0
=

=
0 0 (1 )2
1
0

=
=
2 (1
0 )2 0 (1 )2

So in this situation isothermal back mixing does slow conversion to product

Problems 3-5 are based on the following information

A decomposes in a first order irreversible reaction to form R and S according to the following reaction in
the liquid phase.
() R(l) + S(g)
Pure A at a concentration of 31.7 mol/L is fed ito the reactor system at 6.85kmol/hr and 140 OC. The
reaction rate constant at 140OC is 0.92h-1.
Assume the following data is temperature dependent
heat of reaction of A=-68.7 kJ/kg
heat capacity of A =2.0 kJ/kg*K
heat capacity of R = 2.0kJ/kg*K
molecular weight of A=96.1
molecular weight of R=80.1
molecular weight of S=16.0
3) If the reaction is carried out in an adiabatic PFR with 30.0 cm inside diameter, the reactor length
required to achieve 95% conversion is most nearly
A)
B)
C)
D)

0.0100m
0.170 m
9.95 m
39.8 m

Fundamental equation is =

0
0

= 0 0 so = 0 0

Because reaction is decomposition and is first order:

= 0 (1 )
Now we can set up
0 1
=

0 0 1
0
0
=
ln(1 ) =
ln(0.05)
0
0
6,850
2

=
ln(0.05) = 703.663 = 0.7036633 =

31.7
4
0.92 1

= 9.95
4) What is the exit temperature from the PFR of Problem 3? (Due to its low molecular weight,
ignore component S)
There is an adiabatic system, but an energy balance must be done.

5) Three identical CSTRs are run in series and the total conversion is 95%, the space time for each
reactor is most nearly?
a) 0.688 h
b) 1.58 h
c) 1.86 h
d) 2.45 h
CSTRs in series act like steps, must solve each one individually and then move on to the next.
Reactor 1: 0 =

0 0 0 1 = 1

Solving For CA1:

1 =

0 0
0
=
+ 0 + 1

Now CA1 enters reactor 2:

Reactor 2:
1 1 1 2 = 2
1
2 =
+ 1

Similar balance for the final reactor:

3 =
Subbing in for CA2 and then CA1:

2
+ 1

0
( + 1)3
1
=
(1 + )3

3 =
3
0
Subbing out CA3:

0 (1 )
1
=
(1 + )3
0
1

3
1
1
1
1 3
= [(
) 1] =
) 1] = 1.86
[(
1
0.92 1 0.05

6) Consider the following reaction:

1 2
Assuming first order kinetics, the rate of disappearance of I1 can be expressed as:
Easy problem, only have to remember that the production of a product only depends on the
concentration of its reactants.
Because its rate of disappearance, losing I1 is actually positive in this equation:
1

= 1 + 2 1 + 3 1 + 4 2

1
= 1 (2 + 3 ) 1 4 2

Process Controls
Controls is best explained with examples rather than theory, below is a control loop block diagram
The first things to know is that in control systems there is a:
Process Variable-The variable that you wish to control i.e. temperature of your house, cruise control
speed
Set Point-The point that you wish to control ie 70oC, or 65mph
Manipulated Variable- The variable that changes to alter the process variable i.e. power output of
heater/ac unit, RPMs of the motor
Final Control Elements- The machinery that affects the process variable (solenoid or valve, pump, heater
or cooler, engine)

We will start directly after the process, the process variable is measured. It can be flow, pressure, liquid
level, temperature, composition or any variable that you can measure. The measurement sensor then
sends a feedback signal that checks with the set point. If the set point and feedback signal are identical,
then nothing in the control loop will change. However, if there is an error, then the controller will make
the final control element (valve, solenoid, pump or compressor, heater or cooler) change in a certain
way that will alter the process variable. The cycle will repeat until the process variable meets the set
point.
An open loop system positions the manipulated variable either manually or on a programmed basis. This
operation is used in well-defined processes with little or no disturbances. It is essentially manual mode,
where the user will need to adjust the manipulated variable
A closed loop system uses the measurement of one or more processes to move the manipulated
variable to achieve control. Closed loop systems use feedforward, feedback or both.

Feedback Control- In a feedback control loop, the control variable is compared to the set point Ysp. The
value of the error, E, will make the controller U act in a way to minimize the error. The controller has
tuning parameters related to proportional, integral, derivative, lag, dead time and sampling functions. A
negative feedback will oscillate if the controller gain is too high, but if it is too low, control will be
ineffective. The controller parameters must be properly related to the process parameters to ensure
closed-loop stability while still providing process control.
Feedforward Control- Uses measurements of disturbance variables to position the manipulated variable
in such a way as to minimize any resulting deviation. The disturbance could either be measured loads or
the set point. The feedforward gain must be set precisely to reduce deviation of the controlled variable
from the set point.
Computer Control- Computers have been used to replace analog PID controllers, either by settin set
points of lower level controllers in supervisory control. Single station digital controllers perform PID
control in one or two loops, including computing functions such as mathematical operations. Distributed
control systems provide all these functions.
Dynamic Process Modeling
The simplest way to model a process is with a first order plus dead time model (FOPDT).
In order to complete on of these, the controller output is stepped, generally from the bounds of the
process. The resulting FOPDT dynamic model parameters then are calculated in a correlation to find the
initial estimates of the controller tuning parameters. The tuning parameters are then entered into the
controller, and put in automatic mode.
The above process is done in manual (open loop) mode, then once the parameters are entered in the
controller, it now can be operated in automatic (closed loop) mode.

The equation for the FOPDT dynamic process model is shown below:
()
+ () = ( )

y(t) is the measured process data, and u(t) is the controller output signal.
The model paramets are as shows

Steady state Process gain, KP

The sign of Kp indicates the sense of the controller (positive is reverse acting, negative is direct acting)
Overall Process Time Constant,
Size of indicates wa maximum desirable loop sample time (sample tim T<= 0.1 )
Apparent Dead Time,
In
From the FOPDT step test model
, ()
=
()
The overall process time constant, , describes how fast a measured process variable responds when
forced by a change in the controller output. This constant is found by the following steps.
1) Locate on the plot where the measured process variable first begins to show a clear initial
response to the step change by the controller output. This time is tystart
2) Calculate 63.2% of the total change by the process variable. This is the change not the entire
variable. In essence
63.2 = 0.632
3) Now locate the time on the plot where the process variable reaches y63.2, this is t63.2.
The time constant now is calculated as

= 63.2

Apparent Dead Time,

Dead time is the time that passes the moment the step change in the controller output is made until the
moment when the measured process variable shows a clear initial response to that change. The process
variable will never respond the second the controlled variable is made, so this takes into account the lag
that may occur
=

The limits of FOPDT models are that many processes are nonlinear or time varying, making a linear fit
impractical. However, only computers can fit second order plus dead time models, so in the class room,
FOPDT models are extremely convenient.

P-Only Controller
The simplest controller is the P-only controller. This operates with a proportional multiplier.
() = + ()
The controller starts at the original value ubias, most of the time set by the manufacturer. Controller
error, e(t) is computed every sample time as
() = ()
This is the simplest, cheapest and easiest controller to use. Unfortunately, it is also the least accurate.
The controller can only change from its original value if an error exists. Therefore, if the set point is
changed it will work to reduce the error, but if cannot completely erase the error. If the error was zero,
then the controller value would be back at its original value. P-only controllers can only operate with
offset, so you will never reach the true value of the setpoint.
From the FOPDT model parameters, Kc, can be calculated with ITAE correlation for set point tracking.
1.22
1.08
0.20
0.50
=
=
( )
( )


Reverse Acting, Direct Acting and Control Action
For a process with positive Kp, the process variable increases when the controller output increases.
Therefore, in a closed loop, if the process variable is too high, the controller has to decrease the
controller output signal to correct the error. If the process variable is too low, the controller has to
increase the controller output signal to fix the error. Thus, when a process has a positive Kp, the
controller must be reverse acting. If Kp is negative, the controller is direct acting.
PI Controller
The proportional-integral controller (PI) has the same term as the P-only controller. However, to reduce
offset, an additional tuning parameter, , is introduced. is referred to as reset time. The integral time
calculates the area under the between the set point and process variable and continuously works to
reduce the offset.

() = + () + ()

Here is the laplace form of the PI controller which will be explained later
()
1
= (1 +
)
()

Once again, the major benefit of the PI controller is that it reduces offset. However, the designer needs
to properly tune two terms and the integral term increases the oscillatory behavior of the closed loop
system which may cause significant wear on the controller.
() =

One can set the tuning to three settings:

Aggressive Tuning: 0.1 0.8
Moderate Tuning: 1 8
Conservative Tuing: 10 80

Based off these tuning correlations PI tuning leads to the following

Set Point Tracking:
0.586 0.916
=
( )

1.03 0.165( )

Disturbance Rejection:
0.859 0.977
=
( )

0.68
=
( )
0.674
PID Control
This is the most complex the controller. It contains a proportional, integral and derivative term. For the
sake of the FE we will only discuss the ideal, non-interacting form.

()
() = + () + () +

The Laplace transfer form is

()
1
() =
= (1 +
+ )
()

The integral term addresses how long and how far y(t) is from the set point. However, the derivative
term considers how fast e(t) is changing. The key gain of a PID controller is it reduces the oscillations of a
PI controller. Unfortunately, now a user needs to balance three tuning parameters, and tuning can be
difficult because if one parameter is off, it is difficult to tell exactly which one is responsible for the
performance.
PID Ideal

1 + 0.5
(
)
+ 0.5
= + 0.5

=
2 +

Linearization for Functions of One Variable

Taylor Series Expansions will most likely not be covered in regards to controls, but they will pop up on
the math section of the exam, so they are important to know.
Example: Tank Liquid Level Model
Below is a mass balance on a gravity drained tank
()

= 0 () 1 ()

(0) =

Given in the Problem statement, drain flow is proportional to the square root of hydrostatic head
1

1 () = 2
Now

1
()
+ 2 () = 0 () (0) =

The nonlinear term in the ODE is h1/2(t), It can be isolated using the Taylor series approximation
1
1
1

2 () = 2 + (() )(
(2 ())

This takes into account where h(0)=hs , a basic Taylor Series approximation would use h(0)
Solving:
1
1
1
2 () = 2 + (() )( 1 )
22

Multiplying Out
1
2 ()

1
2

2
1
+ 1 ()
2
22

This can also be applied to equations with multiple variables.

()
= (0 ()) 0 () ()

(0) =

Here the nonlinear term () () is a function of two variables, T(t) and CA(t). We isolate the
nonlinear term and use the taylor series approximation

() () = + (() ) (

(
()
)
+

Deviation variables can be used in preparing equations for control systems

() = (() ) () = ( () )

Laplace Transforms
Laplace Transforms are also incredibly useful in controls.

Here is a quick example of the theory

() =

() = =
0

Integrating by parts where u=t; du=dt =

() = ((

) = ((0 0) ( 2 ) )
) (
0

0
0

() = 2

The theory of Laplace Transforms are not necessarily important, but their uses are important because
they can be applied to transfer functions

From the Laplace table

()
+ () = ( )

(0) = 0

(() (0)) () = ^( )()

With the initial condition y(0)=0
( + 1)() = ()
In order to Put in the Form OF the Transfer Function
()
() =
=
() + 1
The characteristic equation is
+ 1 = 0

Second Order Plus Dead Time Transfer Function

2 ()
dy(t)
()
2

+
2
+
()
=

(0)
=
0,
=0
)

=0
With the Laplace Table we can see that
(0)
2 ( 2 () (0)
) + 2 (sY(s) y(0)) + () = ()

Applying initial conditions

2 2 () + 2 sY(s) + Y(s) = K p ()
Rearranging
()(2 2 + 2n s + 1) = ()
( )
()
() =
= 2 2
() + 2 s + 1
The characteristic equation now is
2 2 + 2n s + 1 = 0

Transfer Functions are shown to us due to their helpfulness in block diagrams, below are the basic
applications:

Show this manipulation using block diagrams: Y(s)=A(s)-B(s)-C(s)

There is always more than one way to solve a problem, but below are two.

Left Photo (A(s)-B(s))-C(s)=Y(s)

Right Photo: Y(s)=A(s)-B(s)-C(s)

() = ()1 ()2 ()

Now we are going to take it up a notch. Below is a closed loop block diagram

() =

()
()
()
() =
() =
()
()
()
()
() =
()

() = () () + () ()
() = ()()
() = ()() = ( () ()) ()
() = () ()
() = () ()() + () ()
Subbing in and solving for Y(s)
()
() () ()
=
() 1 + () () () ()
IN terms of Disturbance
()
()()
=
() 1 + ()() ()

Process Control
Problems 1-3 are based on the following information.
A controlled process is shown in block diagram form in the following illustration. Gp, Gc, Gm, Gn and GD
represent the Laplace domain transfer function of the controlled process, the controller, the
measurement device, the measurement noice in the feedback signal, and the effect of the measured
output disturbance d on the process output y. r is the setpoint signal. u is the output of the controller
and the input of the process.

1) What is the closed loop transfer function describing the effect of d and r on y?

)

a) = (1+

+ (1+ )

b) = + ( )

c) = + (1+

d) = (1+
) +(

1+

Using the shortcut method for the set points effect on y

=
(1 + )
Now the disturbances effect on y

=
1 +
Even though the disturbance does not follow the loop, the denominator is the same for both functions
because it is in closed loop mode.
Summing both
=

(1 + )
1 +

2) In the process in the illustration, Gn=1, Gd=0, Gm=s+1, Gp=1/((2s+1)(s-1)), Gc=K, what values of K
will stabilize this process.
A) K <1
B) K >1
C) K>0.75
D) K>=0
Because GD=0, the disturbance term can be ignored. Substitution now must be implemented
1
( + 1) (
) ()

(2 + 1)( 1)
=
1
1 + ( + 1) (
)
(2 + 1)( 1)
1

Multiplying ((2+1)(1)) by its inverse divided by its inverse =1

( + 1)

=
(2 + 1)( 1) + ( + 1)
Foiling out the bottom yields
2 2 2 + 1 + + = 2 2 + +
It now can be rearranged to look similar to the quadratic equation
2 2 + ( 1) + ( 1) = 2 + +
Borderline stability occurs when s=0
( 1) 2 2 + 1 4(2)( 1)
=0=
2(2)
Using Equation solver
=1
As K increases, the roots remain positive, so the process remains stable for K>1

Refer to the controller process of the following illustration

3( + 1) 3
3 + 1
4( + 1)
=
2 + 1
1
=
+1
= 1
3) Design a realizable feedforward controller, Gff, that transforms the measured disturbance, d,
into a signal that, when added to the feedback controller output, u, counteracts the effect of the
disturbance, d, on the output, y.
=

A) =
B) =
C) =

(24)(+1)

(2+1)(3+1)
4
3+1
( 3) (2+1)
4
( )((3+1) 2 )
3

4
3

2+1
(3+1) 2

D) = ( ) (

2+1

Now there are two paths that the disturbance can take, with the feedforward controller, it adds an
additional term to the first half of the closed-loop transfer function. It is the same method as the
previous problem, just a new path
=(

+
) + (
)
1 + 1 +
1 +

In order to counteract the effect of the disturbance, then the sum of the two terms must equal zero.
+ = 0
=
=
=

4( + 1)
3 + 1

2 + 1
3( + 1) 3

4 (3 + 1) 2
3 (2 + 1)