mol

te H O
2
mol O
2

Section 7: FR&B, Ch. 9 (Energy Balances - III)

Heat of reaction (Section 9.1)

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 Section 7: F&R, Ch. 9 (Energy Balances – III)

2 mol CH OH(v,25oC) 2 mol CH O (g,25oC)

3 2

1 mol O (g,25oC) 2 mol H O (v,25oC)

2 2

2 mol CH OH (l,25oC) 2 mol CH O (g,25oC)

3 2

1 mol O (g,25oC) 2 mol H O (l,25oC)

2 2

The desired heat of reaction is then

(d) How could we calculate a more accurate value of of methanol at 25oC from data in the text?

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 Section 7: F&R, Ch. 9 (Energy Balances – III)

(e) Suppose 200 mol/s of liquid methanol and 30% excess oxygen are fed to a reactor at 25oC, a 50% fractional conversion of methanol is obtained, and the products are brought back
down to 25oC. You wish to calculate . Here is the flow chart.

200 mol CH OH(l)/s _____ mol CH OH(l)/s

3 3
Do a DOF
____ and solve
mol O (g)/sunknowns. Then calculate . Finally, in the space below, write and simplify the energy balance equation and calculate the required rate of heat transfer.
2 _____ mol O (g)/s :
2

______ mol CH O(v)/s

2

______ mol H O(l)/s

2

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Notes with Gaps to accompany Felder, Rousseau, & Bullard, Elementary Principles of Chemical Processes. Copyright ©John Wiley & Sons, Inc.
 Section 7: F&R, Ch. 9 (Energy Balances – III)

Internal energy of reaction

Suppose the reaction in which ethylene is chlorinated to form trichloroethylene

takes place in a batch (closed) reactor at constant volume. The closed system energy balance involves internal energies, not enthalpies, and so we’ll need to evaluate , the internal
energy change when 1 mol of ethylene and 2 mol of chlorine react completely. What we are likely to know, however, is the enthalpy change for that process (the heat of reaction). The
question is, how can we get the first one from the known value of the second one?

 For any system, H = U + PV , and for any change in the system state (including reaction),

or solving for ΔU and applying the result to our reaction process

 In general, for any reaction in which stoichiometric quantities of reactants react completely (which is what is involved when dealing with standard heats of reaction) and the

stoichiometric coefficient of Species i is ,

(Verify that this formula works for the example

reaction.)

If a reaction has no gaseous products or reactants, to a good approximation

Exercise: Write an expression for in terms of and T for the reaction in which gaseous hydrogen fluoride reacts with dissolved silica:

6 HF(g) + SiO (aq)  H SiF (s) + 2H O(l)

2 2 6 2

= __________________________

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 Section 7: F&R, Ch. 9 (Energy Balances – III)

Hess’s Law (Section 9.2)

Hess’s law states that if you can obtain a stoichiometric equation as a linear combination of the stoichiometric equations for other reactions, you can determine its heat of reaction by
performing the same operations on the heats of the other reactions. For example, suppose we experimentally determine the following two standard heats of reaction:

We want to determine the heat of the reaction A  B + 2D but can’t carry out that reaction experimentally. We observe, however, that we can obtain that stoichiometric reaction as
[1] + 2x[2]:
[1] A + B  2C
2x[2] 2C  2B + 2D

Sum A + B + 2C  2C + 2B + 2D  A  B + 2D [3]

Therefore

Hess’s law follows from the fact that enthalpy is a state function. An illustration of how and why it works is given in Section 9.2 of the text.

 Why do we care? Because some reactions cannot be carried out in isolation (that is, without side reactions occurring simultaneously) so that their heat of reaction can’t be
measured directly, but other reactions for which the heat of reaction can be measured can be combined linearly to get the reaction we want. The CO formation reaction
described in Section 9.2 provides an illustration.

 Work through Example 9.2-1 and the Test Yourself that follows it.

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 Section 7: F&R, Ch. 9 (Energy Balances – III)

Calculating Heats of Reaction from Heats of Formation (Section 9.3)

 Formation reaction: A reaction in which a compound is formed from its elemental constituents as they occur in nature [e.g., O (g), and not O]. The standard heat of formation,
2
, is the standard heat of such a reaction. Standard heats of formation of many species are given in Table B.1 or using APEx functions DeltaHfg, DeltaHfl, DeltaHfc, or
DeltaHfaq.

The standard heat of formation of an elemental species [C(s), H (g), O (g),...] is zero.
2 2

 You can use Hess’s law to show that for any reaction a hypothetical process path can be drawn from reactants to elements to products::

Reactants Products
(25oC, 1 atm) (25oC, 1 atm)

Elements
(25oC, 1 atm)

Exercise: Use heats of formation to calculate the standard heat of the reaction:

C H (g)  C H (g) + H (g)

2 6 2 4 2

Solution:
Work through Example 9.3-1 and the Test Yourself that follows it.

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 Section 7: F&R, Ch. 9 (Energy Balances – III)

Calculating Heats of Reaction from Heats of Combustion (Section 9.4)

 Standard heat of combustion: Standard heat of the complete combustion of a fuel to form CO (g) and H O(l) (+ S in fuel  SO , N in fuel  N ), with reactants and products
2 2 2 2
at 25oC and 1 atm. Standard heats of combustion can be found in Table B-1 or using APEx functions DeltaHcg, DeltaHcl, DeltaHcc, or DeltaHcs.

 If a reaction only involves combustible reactants and products, then we can calculate the standard heat of the reaction from tabulated standard heats of combustion. The formula
is

This formula is derived from Hess’s law in the same way that the heat of formation formula was derived:
Reactants Products
25oC, 1 atm 25oC, 1 atm

Combustion products (CO , H O, etc.)

2 2
25oC, 1 atm
Any reactants or products that are themselves combustion products (CO , H O(l), SO …) have a zero heat of combustion. (See Example 9.4-1 for a derivation of the formula
2 2 2
using Hess’s law.)

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 Section 7: F&R, Ch. 9 (Energy Balances – III)

Exercise: Use heats of combustion to calculate the standard heat of the ethane dehydrogenation reaction:

C H (g)  C H (g) + H (g)

2 6 2 4 2

Solution:
How are heats of reaction (including heats of formation and heats of combustion) measured?

Heat of combustion can be measured experimentally in a calorimeter with some known initial temperature and final temperature. Standard heat of combustion can then be determined
by calculating the sensible heat required to bring the reactants from standard conditions to the initial condition in the calorimeter, adding the measured heat of combustion, and then
adding the sensible heat required to bring the products back down to standard conditions. These standard heats of combustion are tabulated in Table B.1, Perry’s Handbook, APEx
functions DeltaHcg, DeltaHcl, DeltaHcc, and DeltaHcs.

Some standard heats of formation (like that of water) can sometimes be measured directly in a calorimeter; others can be determined from standard heats of combustion; still others by
measuring heats of reaction for which all but one heat of formation is known. Those are also tabluated. The standard heat of any reaction can then be determined from either tabulated
heats of formation or heats of combustion.

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 Section 7: F&R, Ch. 9 (Energy Balances – III)

 Energy balance equation for heat of reaction method

The process path that leads to this expression for (recalling that the reference states are the reactants and products at 25oC and 1 atm) is
Reactants (T ) Products (T )
in out
Reactants (25oC) Products (25oC)

 Energy balance equation for heat of formation method:

The process path (recalling that the reference states are the elemental species at 25oC and 1 atm) is
Reactants (T ) Products (T )
in out
Elemental species (25oC)

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 Section 7: F&R, Ch. 9 (Energy Balances – III)

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 Section 7: F&R, Ch. 9 (Energy Balances – III)

Energy balances on reactive processes (Section 9.5)

Use the following procedure for all energy balance problems in Chapter 9. For a batch (closed) reactor, replace “enthalpy” wherever it occurs with “internal energy.”
Given a process description:

1. Draw and label the flow chart. Include all known phases, temperatures, pressures in the labeling, as well as heat and (if there is any) work.

2. Do the degree-of-freedom analysis as usual. If a heat, work, or stream temperature is to be determined, include an energy balance among the equations available to solve for the
unknowns.

3. Write all the system equations except the energy balance. If the problem is to find Q, you should be able to solve them for all other unknowns, but if Q is specified or the system
is adiabatic, you will need to add the energy balance to the set of equations to be solved simultaneously.

4. Prepare an inlet-outlet enthalpy table. Choose reference states (phase, T, and P) for each species in the process in the state (phase, temperature, pressure) for which the heat of
reaction is known. For reactive species, the references may be the species themselves at 25oC and 1 atm (heat of reaction method) or their elemental species in their naturally
occurring states at 25oC and 1 atm (heat of formation method). The heat of reaction method is best used for a single reaction with a known standard heat of reaction; for other
situations, use the heat of formation method.

5. In the table, fill in known and labeled amounts or flow rates from the flow chart. If a species is at its reference state, enter zero for the specific enthalpy. If a species does not
occur at a given inlet or outlet state, cross out the corresponding cells in the table. Label all remaining specific enthalpies or internal energies .

6. Write the energy balance equation (include the heat of reaction term if molecular species were chosen as references, omit it if elemental species were chosen).

7. Write expressions for all of the labeled specific enthalpies by calculating the enthalpy change for the process in which the species goes from its reference state to the process
state. Construct a convenient process state that makes use of the data in the text:

 Tables B.8 and B.9 for enthalpies of combustion gases.

 steam tables for enthalpies of liquid water and steam at high pressures (if you use the steam tables, make your reference state for water liquid at the triple point).

 heat capacities at 1 atm from Table B.2 (use APEx to integrate them), or Kopp’s rule and Table B.10 for a solid or liquid species not listed in Table B.2. If internal
energies are being calculated, use Eqs. (8.3-11) and (8.3-12) to convert C to C .
p v
 heats of fusion and vaporization at the normal boiling point from Table B.1. For species not listed in Table B.1, use one of the estimation formulas on pp. 381–
382.

 heats of mixing and solution at 25oC from Table B.11.

 heats of formation and combustion at 25oC and 1 atm from Table B.1
Unless huge pressure changes from inlet to outlet are involved, ignore the effect of P on specific enthalpy and internal energy. Substitute the expressions in the energy balance.
Solve all equations.

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 Section 7: F&R, Ch. 9 (Energy Balances – III)

Example 1. Ethyl alcohol is produced by fermenting maltose (a sugar) in a continuous fermentation process. The reaction is:

Maltose at 40oC and 50% excess water at 25oC are fed to the process. The maltose reacts completely. The process effluents are liquid ethanol and liquid water at 40oC and carbon
dioxide at 100oC. The standard heat of combustion of maltose to form CO (g) and H O(l) is –5649.1 kJ/mol. Calculate the standard heat of the reaction, and the required net heat
2 2
transfer to or from the process (kJ/100 mol maltose fed), using the heat of reaction method for the energy balance.

Solution:

Since the heat of formation of maltose is not listed in Table B.1 but we do know the heat of combustion, the only way we have of determining the heat of reaction is by using Equation
_________________.

Following the procedure on p. 7-12, we draw and label the flow chart (Step 1), do the degree of freedom analysis (Step 2), and write all equations but the energy balance (Step 3).

Basis: 100 mol/s C H O (s, 40oC)

12 22 11 [mol/s CO (g, 100oC)]
2
[mol/s H O(l, 25oC)](50%XS)
2 [mol/s C H OH(l, 40oC)]
DOF Analysis (base it on extent of rxn balances) 2 5

[mol/s H O(l, 40oC)]

____ unknowns (_________________) 2

- ____ _____________________

- ____ _____________________

- ____ _____________________

- ____ _____________________

= 0 DOF
Determine the values of n , n , n , and n and write them on the chart, and also calculate ξ.
1 2 3 4

= _______ mol/s H O(l) , = _______ mol/s CO (g) , = ________ mol/s C H OH(l)

2 2 2 5

= ________ mol/s H O(l) , ξ: ______________________________________________________

2

Next, prepare the inlet-outlet enthalpy table, using the Heat of Reaction method. Choose reference states for each species appropriate for the heat of reaction method (Step 4), cross out
cells that are not needed, fill in known and labeled n values from the flow chart, put in zero values for specific enthalpies of any species at their reference states, and label all remaining
specific enthalpies (Step 5).

References:

Species
(mol/s) (mol/s)

C H O 100
12 22 11

H O
2

C H OH
2 5

CO
2

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 Section 7: F&R, Ch. 9 (Energy Balances – III)

Now simplify the energy balance equation and substitute the appropriate expression for ΔH.

Finally, write formulas for each of the unknown specific enthalpies. (Hints: You will not find maltose in Table B.2, and from the two points given in Table B.2, (C )
p ethanol(l)
[kJ/(mol oC)] = 0.1031 + 5.57x10–4T.) When the formulas are substituted in the energy balance, all equations can then be solved.

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 Section 7: F&R, Ch. 9 (Energy Balances – III)

Example 2. (Variant of Problem 9.8)

Trichloroethylene, a common degreasing solvent, is produced in the following two-step reaction sequence in a 300-liter batch reactor.

tetrachloroethane

C H (g) + 2Cl (g) C H Cl (l) + H (g)

2 4 2 2 2 4 2

C H Cl (l) C HCl (l) + HCl(g)

2 2 4 2 3

Stoichiometric quantities of ethylene and chlorine are fed to the reactor at 25oC and 2.5 atm. The reactor contents are heated, the reactions proceed, and then the reactor is cooled to a
temperature of 50oC and the vapor contents are analyzed. The results are shown below.

n (mol vapor)
V
Q (kJ)
300 L 0.541 mol H (g)/mol
n [mol C H (g)] 2
o 2 4 n 0.459 mol HCl(g)/mol
(mol liquid)
2n [mol Cl (g)] L
o 2 x [mol50oC
C H Cl (l)/mol]
Calculate the required heat2.5
25oC, transfer
atm to or from the reactor, assuming ideal-gas behavior and using the heat of formation
2 2 4 method for the energy balance.
(1–x) [mol C HCl (l) /mol]
2 3
50oC
Solution

We have already taken the step of drawing and labeling the flow chart, so we next do the DOF analysis, basing it on atomic balances.

____ unknowns (_____________________)

- ____ _____________________________

- ____ _____________________________

- ____ _____________________________

= 0 DOF
Next, write all system equations but the energy balance, using atomic balances. Identify each equation.
(1)

(2)

(3)

(4)

We could solve these equations to determine all unknown variables but _____, but let’s just leave them, write the energy balance, and then solve all of the equations simultaneously.
First, prepare the internal energy table (we have a closed system), remembering that we’re going to use the heat of formation method. Fill in the references, insert blanks and zeroes
where appropriate, fill in molar quantities from the flow chart, and label unknown specific internal energies. Since there are multiple reactions, let’s use the heat for formation method.

References:

Species n (mol) n (mol)

in out

C H (g,25oC) n
2 4 o

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 Section 7: F&R, Ch. 9 (Energy Balances – III)

Cl (g,25oC)
2
H (g,50oC)
2
HCl (g,50oC)

C H Cl (l,50oC)
2 2 4
C HCl (l,50oC)
2 3

Write the energy balance equation, substituting from the table in the expression for ΔU.

(5)

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 Section 7: F&R, Ch. 9 (Energy Balances – III)

Finally, write expressions for all the labeled specific internal energies in terms of physical property data you can find in the text. (Assume that you know the standard heats of formation
of liquid tetrachloroethane and trichloroethylene, which are not in the text.) Remember Eqs. (8.3-11) and (8.3-12) for converting C to C and Eq. (9.1-5) for converting heats of
p v
reaction to internal energies of reaction.

The first expression is given as an illustration:

Table B.1

In writing the remainder of the expressions, you don’t have to write out the process as was done in this case, just the expressions for

(7)

(8)

(9)

(10)

Once the heats of formation and heat capacities are substituted into the expressions, APEx can be used to solve Eqs. (1)–(10) simultaneously.

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 Section 7: F&R, Ch. 9 (Energy Balances – III)

Question: Suppose you are given the standard heats of both reactions:

C H (g) + 2Cl (g) C H Cl (l) + H (g) ,

2 4 2 2 2 4 2

C H Cl (l) C HCl (l) + HCl(g) ,

2 2 4 2 3

How would you calculate the standard heats of formation of tetrachloroethane and trichloroethylene to substitute in Eqs. (9) and (10)?

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 Section 7: F&R, Ch. 9 (Energy Balances – III)

Example 3—Known Q and Unknown Outlet Conditions (Section 9.5b)

Propane at 25oC is burned with 25% excess air at 100oC in a continuous combustion process. Calculate the maximum stack gas temperature that can be achieved.

Solution. Two things happen to the energy released by combustion (i.e., the heat of combustion). Some of it is transferred out of the furnace as heat (Q)—to water inside boiler tubes
that pass through the furnace, for example, or through the exterior furnace wall—and the rest goes to heat the combustion product gas and raise its kinetic energy (the latter effect is
generally negligible).

 The maximum temperature is achieved when:

(a) the reactor is _______________________
and (b) the combustion is ___________________
C H (g) + 5O (g) 3CO (g) + 4H O(l) ,
Basis: 100 mol
3 C83H8 (g) 2 2 2
25% XS air 25oC
 DOF Analysis (based on atomic species balances) Adiabatic

Furnace

____ unknowns (_________________) (Q = 0)

- ____ _____________________

- ____ _____________________

- ____ _____________________

= 0 DOF

 Equations other than energy balance:

(1)

(2)

(3)

(4)

 Extent of reaction: ξ =

 Enthalpy table. Use the heat of reaction method. Note that the reference state for a reactive species must be the state of that species in the reaction for which is known:

References:

Species n (mol) n (mol)

in out

C H (g) 100
3 8

O (g) n
2 o
N (g)
2
CO (g)
2
H O(v)
2

Fill in molar quantities from the flow chart, blank out cells when appropriate and enter known or tabulated values of specific enthalpies, and label unknown specific enthalpies.

 Q: Why can’t you use Table B.8 for outlet enthalpies? A: ___________________________________

 Energy balance. Fill in quantities from the enthalpy table along with the values of ξ and the standard heat of reaction.

(5)

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 Section 7: F&R, Ch. 9 (Energy Balances – III)

 Expressions for unknown enthalpies. Carry out integrations but don’t do any numerical calculations. Note that the heat of vaporization of water at 25oC is given in Equation
9.6-2a as 44.01 kJ/mol.

(6)

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 Section 7: F&R, Ch. 9 (Energy Balances – III)

 The expressions for the specific enthalpies can be substituted into the energy balance [Eq. (5)], which can then be solved simultaneously with Eqs. (1) – (4) for T and the other
unknown variables on the flow chart. (Also see Examples 9.5-3 and 9.5-4.)

Thought Question:

Suppose you had a perfectly insulated gas grill that burns propane.  The H between the feed (propane and air at room temperature) and the outlet (CO and water) is zero at steady
2
state.  How is that possible if the reaction is exothermic?

Solution thermochemistry (Section 9.5c)

We showed in Section 8.5 that considerable energy can be released when some gases and solids dissolve in liquid solvents and when certain liquids (such as strong acids and water) are
mixed together. In the same way, large heats of reaction may be associated with reactions between certain solutions, most notably acid solutions reacting with basic solutions.

 Eq. (9.5-3) defines the standard heat of formation of a solution as the sum of the enthalpy changes for forming a mole of the solute from its elements and then dissolving the
solute in a specified number of moles (or an infinite amount) of the solvent. The units are kJ/mol solute (not per mole of solution).

 The standard heat of a reaction between solutions can be calculated from the standard heats of formation of the reactant and product solutions from Eq. (9.3-1). The procedure is
illustrated in the paragraphs below Eq. (9.5-3) in the text and in Example 9.5-5.

 When you have a reaction between solutions and temperature changes are involved, the calculations can be tricky because the standard heat of reaction is expressed per mole of
solute, while the heat capacity is more likely to be per mole of solution. You just need to keep track of how many moles of each are involved, and make sure you multiply each
specific enthalpy change by the appropriate quantity. Example 9.5-6 illustrates the procedure. Try to follow it—it’s long, but each step is straightforward.

Fuels and Combustion (Section 9.6)

A number of new terms are defined in this section, but the material and energy balance calculations are no different than the ones you’ve done up to now. Here’s what you need to
know.

 Heating value of a fuel (Section 9.6a). The negative of the standard heat of combustion of the fuel (so that it would be positive). The higher heating value presumes liquid
water as one of the combustion products, and the lower heating value presumes water vapor. Eq. (9.6-1) gives the relationship between the two values (which you should be
able to derive), and Eqs. (9.6-2a) and (9.6-2b) give the heat of vaporization of water at 25oC (which is needed to calculate a higher heating value from a lower heating value or
vice versa). See Example 9.6-1 and the Test Yourself on p. 521.

 Adiabatic flame temperature (Section 9.6b). The temperature that would be attained in a combustion furnace if the reactor is adiabatic and combustion is complete—which is to
say, the maximum temperature that can be achieved for the given inlet conditions. Example 3 on pp. 7-19 and 7-20 of this handout illustrates the calculation of an adiabatic
flame temperature, as does Example 9.6-2. Note that APEx is ideally suited to this calculation, which requires trial-and-error solution if a manual method is used.

 Flammability and ignition (Section 9.6c) and flames and detonations (Section 9.6d). These sections consist entirely of definitions and explanations of phenomena that come up
in both engineering practice and everyday life (e.g., what is a flame?). Learning them equips you to impress your friends and loved ones by being able to explain them, and also
helps you avoid the embarrassment of being an engineer and not knowing how to explain them if someone asks you. You should be able to explain the difference between

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 Section 7: F&R, Ch. 9 (Energy Balances – III)

oxidation and combustion (burning), the concepts of ignition and autoignition temperature, the lower and upper flammability limits and explosive range of a fuel, a flame
(exactly what is it?), flame velocity, stationary flame, and flashback, the difference between a blue flame and a yellow flame, and detonations and shock waves.

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 Section 7: F&R, Ch. 9 (Energy Balances – III)

If you reached the last page of the coursepack (or wherever your instructor stopped for the semester), then it’s time to celebrate! Look back at the early chapters – those things
you might have struggled with initially (drawing the flowchart, labeling the flowchart, degree of freedom analysis, writing a material balance equation) should be second nature
to you now. You’re comfortable with reading what looks like a complicated word problem, translating it into a diagram, and translating that diagram into equations, which you
can then solve to get the requested information. You look at the world differently now because you connect it to things you’ve learned in this course – mass balances, vapor-
liquid equilibria, phase changes, energy balances, colligative properties, and others. (Just think of all the interesting tidbits you can drop at family dinners or student parties!)
As you proceed to future engineering courses, you’ll go into more detail about things you’ve learned here, and you’ll start to challenge some of the assumptions that we’ve
made about systems being ideal or at steady state. Each engineering course you take will serve as the foundation for the next one, and you’ll find that you will continue to build
on this material in future courses. Enjoy the rest of the journey!

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