1.

INTRODUCTION
How are Chemical Engineers Able
to Solve Such a Broad Array of
Problems?

Chemical engineers work in a wide array of disciplines and applications: chemicals, refining,
polymers, food, pharmaceuticals, bioprocesses, microelectronics, etc., etc., etc.

How in the world are they able to learn and understand all that is needed to do this?

Answer: We use a common approach to understanding disciplines and solving

problems that is based on fundamental scientific laws coupled with some fundamental
definitions, a fundamentals-based understanding of material properties and process design
including economics, and facility with mathematics as both a language and a problem solution
tool. But, the heart of it all is the fundamental laws

Elements of chemical engineering background: science (math, physics, chemistry, biology),

engineering, economics, communications)

What ARE these really important

laws?

Conservation of mass

Conservation of energy

Conservation of (linear) momentum

Conservation of angular momentum

The Second Law of Thermodynamics

There is a conceptual structure to

the laws
Fortunately for our feeble brains, these laws all follow exactly
the same structure. Thus, we start developing our
understanding of them by formulating a firm understanding of
this structure.

This structure seems easy

This structure is one that you are already familiar with

But, dont let these facts lull you into a false sense of accomplishment! Dont think that you
already understand the laws. Understanding the structure, framework, is necessary to
understanding each of the laws but it is not sufficient.

In addition to the framework, you must understand import issues of material properties,
process design and mathematics.

So, what is the structure of the

laws?

All of these important Laws follow an accounting concept that is identical to keeping track of
the money in your bank account.

The basic idea is that the $ balance of the account changes over time because of deposits and
withdrawals (including any service charges, fees, or interest earnings)

In order to prove (reconcile) the account balance, you must agree

that you are counting U.S. dollars (e.g., as opposed to pounds sterling, euros, yen,
yuan, baht, etc.)

which account you are reconciling, and

the time period over which you are counting deposits, withdrawals, and observing the
account balance.

2. The (Bank Account)

Accounting Equation
Imagine your bank account, into which you make deposits and
from which you make withdrawals. In addition, your account
may earn interest or you may have service charges (We make
sketches all the time to help us visualize what is happening in a
process. These sketches are very important to our problemsolving process.):

(Interest and service charges are input and output, not

generation or consumption as they are transfers between your
account and the bank.) Now, think about how you reconcile
your account balance at the end of the month with the
statement from your bank. This process works like this (the
time period is the month which your statement covers):

Hopefully, you are well aware of this balance concept and are adept at keeping your account
balance in the black!

Note that each of the three issues must be the same in each term: $, account, and time
period. It will not work for you to calculate one term over one time period and another term

over a different time period! Nor will it work to count $ in one term and Euros in another. Nor
will it work for one term to be for one account and a second term to apply to a different
account!

Note the definition of accumulation of $ in terms of the amount in the account and the end
and beginning of the time period. We would all like for accumulation in our accounts to be
positive!

3. The (Fundamental Laws)

Accounting Equation Definitions

We use an analogous accounting process in engineering.

To make the accounting, we must first define three things: 1) the item to be counted
(the Extensive Property, EP), 2) the time period, 3) a surface boundary that divides the
universe into two parts: the system and the surroundings.

Some Possible Extensive Properties:

Total Energy

Total Mass

Net Electrical Charge

Positive Charge

Negative Charge

Linear Momentum

Angular Momentum

Species Mass (compounds, ions, free radicals, etc.)

Elements (Na, O, N, etc.)

Forms of energy that are subsets of total energy: thermal energy, mechanical energy

The (Fundamental Laws)

Accounting Equation Verbal
Statement
Now imagine a portion of the universe (which we call the
system) in which you wish to keep track of the amount of a
certain extensive property (EP). A sketch would show the
system, entering and leaving EP, and (if possible for it to occur)
generation and consumption of the EP inside the system:

Note that it is typical for the sketch to explicitly identify the

system boundary so as to clearly define input and output flows
into and out of the system.
The the verbal statement of the accounting equation
(analogous to your bank account balancing verbal equation) is:

Note that this statement includes the possibility that the EP is

generated or consumed. For example, water, a chemical
compound, may be generated or consumed by chemical
reaction.

Also note that the definition of accumulation with the system is

completely analogous to accumulation of dollars in your bank
account.

Further Comments on the

Accounting Equation and the
Fundamental Laws

While many EPs can be counted, only a (handful + one) produce laws.

Whether a law is associated with an EP is determined by whether or not there are fundamental
constraints on generation or consumption of the EP.For example:
o

Total mass is neither generated nor consumed Total Mass is a conserved EP

Total energy is neither generated nor consumed Total Energy is a conserved EP

Linear momentum is neither generated nor consumed Linear Momentum is a

conserved EP

Angular momentum is neither generated nor consumed Angular Momentum is a

conserved EP

Net electrical charge is neither generated nor consumed Net Electrical Charge is a
conserved EP

Entropy is

never

consumed although

it

may be

generated

Entropy is not

conserved BUT there is a special constraint on its generation (generation > 0)

So, counting the following properties produces a fundamental law: total mass, total energy,
linear momentum, angular momentum, net charge, entropy

Five of these EPs produce Conservation Laws; the sixth EP yields the Second Law of
Thermodynamics

N.B.: Of course, these laws are defined in our normal

engineering world of negligible nuclear conversions and
relativistic effects on mass and energy.
4. CONSERVATION OF MASS
Now, imagine a process with mass entering and leaving. A
process sketch might look like this:

Interesting, isnt it, that this sketch looks so much like the bank
account sketch and the general EP sketch!

For any portion of the universe (the System), defined by a boundary (that may be moving or
stationary), and over any prescribed amount of time (the Time Period), conservation of total
mass requires:

Mass may enter or leave in the form of mass possessed by mass. (This sounds trivial, but
see the next laws.)

Because total mass is conserved, there are no generation or consumption terms.

Because the elements are also conserved, an element conservation law looks exactly like the
total mass equation above; simply change total mass to the element being counted

5.CONSERVATION OF NET CHARGE

For any portion of the universe (the System), defined by a boundary (that may be moving or
stationary), and over any prescribed amount of time (the Time Period), conservation of net
electrical charge requires:

Net charge may enter or leave in the form of charge possessed by mass (ions, electrons, etc.).

Net charge is conserved, so there are no net generation or consumption terms. However, there
may be generation of positive and negative charges (dissolution of a salt to produce a cation
and an anion, e.g.) separately, that total to zero net charge generation.

6.CONSERSATION OF ENERGY

Now, imagine a process with energy entering and leaving. Note

that energy is conserved so there cannot be any energy
generation or consumption inside the system. A simple process
sketch might look like this:

For any portion of the universe (the System), defined by a boundary (that may be moving or
stationary), and over any prescribed amount of time (the Time Period), conservation of total
energy requires:

Energy may enter or leave in the form of energy possessed by mass, heat transfer, or work

Because total energy is conserved, there are no generation or consumption terms.

7.Conservation of Linear Momentum

Now, imagine a process with (linear) momentum entering and
leaving. Note that momentum is a conserved property so there
cannot be any momentum generation or consumption inside
the system. A simple process sketch might look like this:

For any portion of the universe (the System), defined by a boundary (that may be moving or
stationary), and over any prescribed amount of time (the Time Period), conservation of
(linear) momentum requires:

Momentum may enter or leave in the form of momentum possessed by mass or by the action
of external forces, or even by the momentum possessed by electromagnetic radiation

Because momentum is conserved, there are no generation or consumption terms. This means,
for example, that external forces exchange momentum between the system and its
surroundings; they do not generate or consume momentum.

8. Conservation of Angular Momentum

Now, imagine a process with angular momentum entering and
leaving. Note that angular momentum is a conserved property
so there cannot be any angular momentum generation or
consumption inside the system. A simple process sketch might
look like this:

For any portion of the universe (the System), defined by a boundary (that may be moving or
stationary), and over any prescribed amount of time (the Time Period), conservation of
angular momentum requires:

Angular Momentum may enter or leave in the form of angular momentum possessed by mass
or by the action of external torques

Because angular momentum is conserved, there are no generation or consumption terms.

9. The Second Law of

Thermodynamics
Now, imagine a process with entropy entering and leaving.
(Entropy is the thermodynamic property of matter that is used
to quantify the Second Law of thermodynamics, i.e., to quantify
the natural directionality of spontaneous events.) Note that
entropy is NOT a conserved property although it does have a
constraint on its generation (entropy generation is positive or
zero) in that there cannot be any entropy consumption (but
there may be generation). A simple process sketch might look
like this:

For any portion of the universe (the System), defined by a boundary (that may be moving or
stationary), and over any prescribed amount of time (the Time Period), The Second Law of
Thermodynamics requires:

Entropy may enter or leave in the form of entropy possessed by mass and by heat transfer

Entropy may be generated (and hence there is a generation term in the equation) within the
system by processes that constitute a move towards equilibrium such as: equilibration of
temperature (moving towards uniform temperature), equilibration of concentration (moving
towards uniform concentration in a single phase), dissipation of mechanical energy through
friction

Note again that entropy cannot be consumed; entropy generation cannot be negative!

10.Final Thoughts
Counting Non-Conserved
Properties

There is no reason we cant count EPs that are not conserved (i.e., there may be generation
and/or consumption). The equations obtained may be very helpful; they just are not special in
that they dont make laws.

Counting non-conserved properties must be done subject to the constraints of the above
conservation laws and the Second Law of Thermodynamics

Examples:

Species (compounds, ions, free radicals, etc.) mass balances (used extensively to
analyze chemical processes, including reacting systems)

Thermal energy balance (heat balance)

Mechanical energy balance (used extensively in fluid mechanics)

Some Additional Accounting Law

Concepts

If accumulation is zero (no change in the EP in the system), then the system is said to be at
Steady State and it is a steady-state process.

If the accumulation is not zero, then the system is at unsteady state and it is an unsteadystate process.

If the system size is differential and the system properties may be represented by continuous
mathematical functions of position and time, then we refer to this scale as the continuum
scale.

If the system size is small enough that we must consider discrete molecules, then we classify
this as a molecular scale (of the order of angstroms, 10 -10 m).

Between the molecular and continuum scales lies the nano scale (of the order of nanometers,
10-9 m)

If the system size is big enough that whole process units comprise the system (e.g. distillation
column), then we call this the macroscopic scale or a unit operations scale.

If the system size encompasses an entire chemical process plant or several plants (e.g., an
entire refinery), then is would be an integrated plant scale.

Closing Thoughts

Dont underestimate the importance of understanding the details of these laws outlined above
by the seeming simplicity of their verbal (conceptual) statements; always keep in mind the
importance of the definitions of system, time period, and extensive property.

Applying these concepts to problems requires delving into more details of mass, energy,
thermodynamic properties, heat, work, process descriptions, specific examples, and more.
Presenting these details comprises the chemical engineering curriculum! See the ICCs for each
of these EPs for some additional information.