# ![](media/image1.png){width="2.7090277777777776in" height="0.8in"}

#  {#section-1 .Title1}

# Chemical Processing {#chemical-processing .Title1}

#  {#section-2 .Title1}

#  {#section-3 .Title1}

# Qualification Standard Reference Guide {#qualification-standard-reference-guide .Title1}

# [May 2006]{.smallcaps} {#may-2006 .Title1}

PURPOSE [1](#purpose)

SCOPE [1](#scope)

TECHNICAL COMPETENCIES [2](#technical-competencies)

1\. Chemical processing personnel shall have a working-level knowledge
of the operation of chemical processes.
[2](#chemical-processing-personnel-shall-have-a-working-level-knowledge-of-the-operation-of-chemical-processes.)

2\. Chemical processing personnel shall demonstrate an expert-level
knowledge of mass transfer and mass balances.
[6](#chemical-processing-personnel-shall-demonstrate-an-expert-level-knowledge-of-mass-transfer-and-mass-balances.)

3\. Chemical processing personnel shall demonstrate an expert-level
knowledge of stoichiometry and reaction kinetics.
[18](#chemical-processing-personnel-shall-demonstrate-an-expert-level-knowledge-of-stoichiometry-and-reaction-kinetics.)

4\. Chemical processing personnel shall demonstrate an expert-level
knowledge of process safety.
[22](#chemical-processing-personnel-shall-demonstrate-an-expert-level-knowledge-of-process-safety.)

5\. Chemical processing personnel shall demonstrate a working-level
knowledge of DOE Safety Basis requirements.
[30](#chemical-processing-personnel-shall-demonstrate-a-working-level-knowledge-of-doe-safety-basis-requirements.)

6\. Chemical processing personnel shall demonstrate a working-level
knowledge of safety and relief devices.
[33](#chemical-processing-personnel-shall-demonstrate-a-working-level-knowledge-of-safety-and-relief-devices.)

7\. Chemical processing personnel shall demonstrate working-level
knowledge of general piping systems.
[35](#chemical-processing-personnel-shall-demonstrate-working-level-knowledge-of-general-piping-systems.)

8\. Chemical processing personnel shall demonstrate a working-level
knowledge of mechanical diagrams, including:
[36](#chemical-processing-personnel-shall-demonstrate-a-working-level-knowledge-of-mechanical-diagrams-including)

9\. Chemical processing personnel shall demonstrate a working-level
knowledge of the general construction, operation, and theory of valves.
[37](#chemical-processing-personnel-shall-demonstrate-a-working-level-knowledge-of-the-general-construction-operation-and-theory-of-valves.)

10\. Chemical processing personnel shall demonstrate a working-level
knowledge of measurement, data collection, and analysis.
[41](#chemical-processing-personnel-shall-demonstrate-a-working-level-knowledge-of-measurement-data-collection-and-analysis.)

11\. Chemical processing personnel shall demonstrate a working-level
knowledge of pump theory and operation.
[47](#chemical-processing-personnel-shall-demonstrate-a-working-level-knowledge-of-pump-theory-and-operation.)

12\. Chemical processing personnel shall demonstrate a working-level
knowledge of fluid mechanics and properties.
[51](#chemical-processing-personnel-shall-demonstrate-a-working-level-knowledge-of-fluid-mechanics-and-properties.)

13\. Chemical processing personnel shall demonstrate the ability to
calculate flow rates in fluid systems.
[53](#chemical-processing-personnel-shall-demonstrate-the-ability-to-calculate-flow-rates-in-fluid-systems.)

14\. Chemical processing personnel shall demonstrate a working-level
knowledge of thermodynamics.
[53](#chemical-processing-personnel-shall-demonstrate-a-working-level-knowledge-of-thermodynamics.)

15\. Chemical processing personnel shall demonstrate a working-level
knowledge of steady-state heat transfer.
[55](#chemical-processing-personnel-shall-demonstrate-a-working-level-knowledge-of-steady-state-heat-transfer.)

16\. Chemical processing personnel shall demonstrate a working-level
knowledge of the construction and operation of heat exchangers.
[56](#chemical-processing-personnel-shall-demonstrate-a-working-level-knowledge-of-the-construction-and-operation-of-heat-exchangers.)

17\. Chemical processing personnel shall demonstrate a working-level
knowledge of the components, operation, and theory of pneumatic systems.
[58](#chemical-processing-personnel-shall-demonstrate-a-working-level-knowledge-of-the-components-operation-and-theory-of-pneumatic-systems.)

18\. Chemical processing personnel shall demonstrate a working-level
knowledge of the basic components, operations, and theory of hydraulic
systems.
[59](#chemical-processing-personnel-shall-demonstrate-a-working-level-knowledge-of-the-basic-components-operations-and-theory-of-hydraulic-systems.)

19\. Chemical processing personnel shall demonstrate a working-level
knowledge of Project and Contract Management.
[61](#chemical-processing-personnel-shall-demonstrate-a-working-level-knowledge-of-project-and-contract-management.)

20\. Chemical Processing Personnel shall demonstrate a familiarity-level
of knowledge of Software Quality Assurance relationships between the
problems being addressed by safety analysis and design codes, the design
requirements for the codes, and the components of the codes.
[75](#chemical-processing-personnel-shall-demonstrate-a-familiarity-level-of-knowledge-of-software-quality-assurance-relationships-between-the-problems-being-addressed-by-safety-analysis-and-design-codes-the-design-requirements-for-the-codes-and-the-components-of-the-codes.)

21\. Chemical Processing Personnel shall demonstrate a familiarity-level
of knowledge of Software Quality Assurance functional interfaces between
safety system software components and the system-level design.
[76](#chemical-processing-personnel-shall-demonstrate-a-familiarity-level-of-knowledge-of-software-quality-assurance-functional-interfaces-between-safety-system-software-components-and-the-system-level-design.)

Selected Bibliography and Suggested Reading
A-[1](#selected-bibliography-and-suggested-reading)

# PURPOSE

The purpose of this reference guide is to provide a document that
contains the information required for a National Nuclear Security
Administration (NNSA) technical employee to successfully complete the
Chemical Processing Functional Area Qualification Standard. In some
cases, information essential to meeting the qualification requirements
is provided. Some competency statements require extensive knowledge or
skill development. Reproducing all the required information for those
statements in this document is not practical. In those instances,
references are included to guide the candidate to additional resources.

# SCOPE

This reference guide has been developed to address the competency
statements in the January 2004 edition of DOE-STD-1176-2004, Chemical
Processing Functional Area Qualification Standard. Competency statements
and supporting knowledge and/or skill statements from the qualification
standard are shown in contrasting bold type, while the corresponding
information associated with each statement is provided below it. The
qualification standard for Chemical Processing contains 21 competency
statements.

Every effort has been made to provide the most current information and
references available as of May 2006. However, the candidate is advised
to verify the applicability of the information provided.

Please direct your questions or comments related to this document to the
NNSA Training and Development Department.

# TECHNICAL COMPETENCIES

## Chemical processing personnel shall have a working-level knowledge of the operation of chemical processes.

a)  Identify the light and heavy phases, and discuss the direction of
    mass transfer or separations aspects of the following unit
    operations:

-   Solvent Extraction (Extractant, Raffinate, Emulsions, Coalescence,
    Countercurrent multistage contactor, Extraction/Scrubbing/Stripping,
    Partition Coefficient, Efficiency)

-   Gas Absorption/Stripping

-   Ion Exchange

-   Adsorption

-   Filtration

-   Evaporation

-   Crystallization

-   Sedimentation

-   Leaching

### Solvent Extraction

Solvent extraction is a useful method to separate components (compounds)
of a mixture. The success of this method depends upon the difference in
solubility of a compound in various solvents. Solvent extraction is
based on the transfer of a solute from one liquid phase into another
liquid phase. Extraction becomes a very useful tool if you choose a
suitable extraction solvent. You can use extraction to separate a
substance selectively from a mixture, or to remove unwanted impurities
from a solution.

In practical use, usually one phase is water or a water-based (aqueous)
solution and the other an [organic
solvent](http://en.wikipedia.org/wiki/Organic_solvent) which is
[immiscible](http://en.wikipedia.org/wiki/Immiscible) with water. It is
interesting to note that solvent extraction is possible in non-aqueous
systems; for instance, in a system consisting of a [molten
metal](http://en.wikipedia.org/w/index.php?title=Molten_metal&action=edit)
in contact with [molten](http://en.wikipedia.org/wiki/Molten) salt,
metals can be extracted from one phase to the other.

In solvent extraction, a distribution ratio is often quoted as a measure
of how well-extracted a species is (efficiency). The distribution ratio
(sometimes referred to as the partition coefficient) is equal to the
concentration of a solute in the organic phase divided by its
concentration in the aqueous phase. Depending on the system, the
distribution ratio can be a function of temperature, the concentration
of chemical species in the system, or a large number of other
parameters.

Typically an industrial process will use an extraction step in which
solutes are transferred from the aqueous phase to the organic phase.
This is often followed by a scrubbing stage in which unwanted solutes
are removed from the organic phase, and then a stripping stage in which
the wanted solutes are removed from the organic phase. The organic phase
may then be treated to make it ready for use again.

After use, the organic phase may be subjected to a cleaning step to
remove any degradation products. For instance, in PUREX plants, the used
organic phase is washed with sodium carbonate solution to remove any
dibutyl hydrogen phosphate or butyl dihydrogen phosphate that might be
present.

The following are some common terms used in solvent extraction:

-   Solvent is the term for the organic layer.

-   Extractant is the term for a metal extraction agent.

-   Raffinate is the term for the aqueous layer after a solute has been
    extracted from it.

-   Emulsion is a mixture of two immiscible (unblendable) substances.

-   Coalescence is the process by which two or more droplets or
    particles merge during contact to form a single daughter droplet (or
    bubble).

-   Extraction is a method to separate components of a mixture.

-   Scrubbing is the term for the back extraction of an unwanted solute
    from the organic phase.

-   Stripping is the term for the back extraction from the organic
    phase.

-   Partition coefficient is a measure of the differential solubility of
    a compound in two solvents.

### Gas Absorption/Stripping

Gas absorption is a mass transfer operation in which a gas mixture is
contacted with a liquid to preferentially absorb one or more of the
components of the gas stream. This operation is found in many industries
for the recovery of valuable products and the cleaning of exhaust or
vent streams. If necessary, the solute can be recovered from the
absorbing liquid by distillation and the liquid can be recycled or it
can be discarded completely. In some cases, a solute is removed from a
liquid by contacting it with a gas. This operation is the reverse of gas
absorption and is called desorption or gas stripping.

### Ion Exchange

Ion exchange is a process in which ions are exchanged between a solution
and an ion exchanger --- an insoluble solid or gel. Typical ion
exchangers are ion exchange resins, zeolite, montmorillonite, clay, and
humus. Ion exchangers are either cation exchangers for positively
charged cations or anion exchangers for negatively charged anions. Ion
exchange is a reversible process, and the ion exchanger can be
regenerated or loaded by washing with an excess of the ions to be
exchanged. Ion exchange is a method widely used in household and
industrial water purifications to produce soft water. This is
accomplished by exchanging calcium (Ca^2+^) and magnesium (Mg^2+^)
cations against sodium (Na^+^) or hydrogen (H^+^) cations.

The process works as follows. Ion exchange resins (little beads that are
charged) are coated with the replacement ions. In the case of water
softening, the beads are coated with Na^+^ and Cl^-^. In the case of
deionization, they are coated with H^+^ and OH^-^. Water flows over the
resin. The ions in the water are attracted to the resin. The ions in the
water attach themselves to the resin and knock off the ions that are
already attached.

The resin is exhausted when all of the replacement ions are gone. In
order to replenish the resin, also called regenerating the resin, a
strong solution of the replenishment ions must be applied to the resin.
This removes the ions that came from the water and regenerates the
resin. The solution that is used to regenerate water softeners is
concentrated salt water called brine. There are two solutions that are
used to regenerate a deionizer. One is a concentrated acid, and the
other is a concentrated base.

### Adsorption

Adsorption is a chemical process that takes place when a liquid or, most
commonly, a gas (adsorbate) accumulates on the surface of a solid
(adsorbent), forming a molecular or atomic film.

Adsorption, similar to surface tension, is a consequence of surface
energy. Consider a clean surface exposed to a gaseous atmosphere. In the
bulk material, all the bonding requirements (be they ionic, covalent, or
metallic) of the constituent atoms of the material are filled. However,
atoms on the surface experience a bond deficiency because they are not
wholly surrounded by other atoms. It is then energetically favorable for
these dangling bonds to react with whatever happens to be available. The
exact nature of the bonding depends on the details of the species
involved, but the adsorbed material is generally classed as
experimenting physisorption or chemisorption.

### Filtration

There are many different methods of filtration, but all aim to attain
the separation of two or more substances. This is achieved by some form
of interaction between the substance or objects to be removed and the
filter. In addition, the substance that is to pass through the filter
must be a fluid, i.e., a liquid or a gas. Filtration is a more efficient
method for the separation of mixtures than decantation, but is much more
time consuming. If very small amounts of solution are involved, most of
the solution may be soaked up by the filter medium.

The simplest method of filtration is to pass a solution of a solid and
fluid through a porous interface so that the solid is trapped while the
fluid passes through. This principle relies on the size difference
between the particles making up the fluid and the particles making up
the solid.

For separation where there is a very small size difference, chemical
filters may be used. These filters have properties that enable
undesirable items to be attracted and retained by the filter, while the
fluid from which they are to be separated is not. Filters of this kind
most often take the form of electrostatic attractions. These forms of
filters may become clogged, or the active sites on the filter may all be
used up by the undesirable particles being filtered. However, most
chemical filters are designed so that the filter can be flushed with a
chemical that will remove the undesirable particles and allow the filter
to be reused.

One disadvantage of the physical barrier method of filtration is that
the substance being filtered from the fluid will clog the channels of
the filter over time, causing the filter to become less and less
efficient (e.g., a vacuum cleaner bag). Thus, methods have been
developed to prevent this from happening. Most such methods involve
replacing the filter. However, if the filter is needed for a continuous
process, this is highly problematic and complex scraping and in-situ
cleaning mechanisms have to be used.

### Evaporation

Evaporation is the process whereby atoms or molecules in a liquid state
(or solid state if the substance sublimes) gain sufficient energy to
enter the gaseous state.

The thermal motion of a molecule of liquid must be sufficient to
overcome the surface tension and evaporate, that is, its kinetic energy
must exceed the work function of cohesion at the surface. Evaporation
therefore, proceeds more quickly at higher temperatures, at higher flow
rates between the gaseous and liquid phases, and in liquids with lower
surface tension (i.e., higher vapor pressure). Since only a small
proportion of the molecules are located near the surface and moving in
the proper direction to escape at any given instant, the rate of
evaporation is limited. Also, as the faster-moving molecules escape, the
remaining molecules have lower average kinetic energy, and the
temperature of the liquid therefore decreases. This phenomenon is called
evaporative cooling. One example for evaporative cooling is sweating.

Gas has less order than liquid or solid matter, so the entropy of the
system is increased, which always requires energy input. This means that
the enthalpy change for evaporation (ΔH~evaporation~) is always
positive.

Evaporation is a critical component of the water cycle, which is
responsible for clouds and rain. Solar energy drives evaporation of
water from oceans, lakes, moisture in the soil, and other sources of
water. In hydrology, evaporation and transpiration (which involves
evaporation within plant stomata) are collectively termed
evapotranspiration.

### Crystallization

Crystallization is a solid-liquid separation technique, or the process
of formation of solid crystals from a homogeneous solution.

For crystallization to occur, the solution at hand ought to be
supersaturated. Put simply, the solution should contain more solute
molecules than it would under ordinary conditions. This can be achieved
by various methods --- solvent evaporation, cooling, chemical reaction,
and drowning being the most common ones used in industrial practice.

For example, if you take a bowl of water and add sugar crystals to it
until no more crystals can be dissolved, the solution becomes saturated.
You can dissolve further crystals into this saturated solution by
heating it, because the solubility of solutes generally increases with
temperature. When the temperature of the solution is allowed to attain
equilibrium with the surroundings, the solubility of the solute
decreases (because the temperature of the solution has decreased) and
the excess sugar so added crystallizes out.

This process illustrates the simplest of super-saturation techniques.
Drowning is the addition of a non-solvent in the solution that decreases
the solubility of the solid. Alternatively, chemical reactions can also
be used to decrease the solubility of the solid in the solvent, thus
working towards super-saturation.

Crystallization can be divided into primary and secondary nucleation.
Primary nucleation is the growth of a new crystal, which in turn causes
secondary nucleation. Secondary nucleation is the main stage in
crystallization for this is what causes the mass production of crystals.
Secondary nucleation requires existing crystals to perpetuate crystal
growth. In our sugar example, we had obtained such nuclei when the
excess sugar had just about crystallized out, assisting further crystal
formation.

### Sedimentation

Sediment is any particulate matter that can be transported by fluid flow
and which eventually is deposited as a layer of solid particles on the
bed or bottom of a body of water or other liquid. Sedimentation is the
deposition by settling of a suspended material.

Sediments are also transported by wind (eolian) and glaciers. Desert
sand dunes and loess are examples of eolian transport and deposition.
Glacial moraine deposits and till are ice transported sediments. Simple
gravitational collapse also creates sediments such as talus and mountain
slide deposits, as well as karst collapse features.

Seas, oceans, and lakes accumulate sediment over time. The material can
be terrigenous (originating on the land) or marine (originating in the
ocean). Deposited sediments are the source of sedimentary rocks, which
can contain fossils of the inhabitants of the body of water that were,
upon death, covered by accumulating sediment. Lake bed sediments that
have not solidified into rock can be used to determine past climatic
conditions.

### Leaching

Leaching is the process of extracting a substance from a solid by
dissolving it in a liquid. In the chemical processing industry, leaching
is known as extraction. Leaching has a variety of commercial
applications, including separation of metal from ore using acid, and
sugar from beets using hot water.

In agriculture, leaching may refer to the loss of water-soluble plant
nutrients from the soil due to rain and irrigation. Soil structure, crop
planning, type and application rates of fertilizers, and other factors
are taken into account to avoid excessive nutrient loss. Leaching may
also refer to the practice of applying a small amount of excess
irrigation where the water has a high salt content to avoid salts from
building up in the soil. Where this is practiced, drainage must also
usually be employed to carry away the excess water.

Leaching is an environmental concern when it contributes to groundwater
contamination. As water from rain, flooding, or other sources seeps into
the ground, it can dissolve chemicals and carry them into the
underground water supply. Of particular concern are hazardous waste
dumps and landfills, and in agriculture, excess fertilizer and
improperly stored animal manure.

## Chemical processing personnel shall demonstrate an expert-level knowledge of mass transfer and mass balances.

a)  Discuss the ideal gas law as it applies to pressure, volume, and
    temperature relationships.

The ideal gas law is the equation of the state of an ideal gas. The
state of an amount of gas is determined by its pressure, volume, and
temperature. The equation has the form

PV = nRT

where:

P = pressure

V = volume

n = number of moles of gas

R = gas constant

T = temperature

The ideal gas law is most accurate for monoatomic gases and is favored
at high temperatures and low pressures. It does not factor in the size
of each gas molecule or the effects of intermolecular attraction.

b)  Discuss the application of mass balances and provide an example of
    an application in plant chemical flowsheets.

*Mass Balances*

A mass balance (also called a material balance) is an accounting of
material entering and leaving a system. Fundamental to the balance is
the conservation of mass principle, i.e., that matter cannot disappear
or be created. Mass balances are used to design chemical reactors,
analyze alternative processes to produce chemicals, in pollution
dispersion models, etc. In environmental monitoring, the term "budget
calculations" is used to describe mass balance equations where they are
used to evaluate monitoring data (comparing input and output, etc.).

The mass that enters a system must (conservation of mass principle)
either leave the system or accumulate within the system, i.e.:

IN = OUT + ACC

where IN denotes what enters the system, OUT denotes what leaves the
system, and ACC denotes accumulation within the system (which may be
negative or positive). Mass balances are often developed for total mass
crossing the boundaries of a system, but they can also focus on one
element (e.g., carbon) or chemical compound (e.g., water). When mass
balances are written for specific compounds, number of individuals in a
population, etc., rather than for the total mass of the system, a
production term (PROD) is introduced such that

IN + PROD = OUT + ACC

The production term may then describe chemical reaction rates, the
difference between births and deaths, etc. PROD might be positive or
negative, just as for ACC.

Mass balances are either integral mass balances or differential mass
balances. An integral mass balance is a black box approach and focuses
on the overall behavior of a system, whereas a differential mass balance
focuses on mechanisms within the system (which in turn affect the
overall behavior).

To make an integral mass balance, one must first identify system
boundaries, i.e., how the system is connected to the rest of the world
and how the rest of the world influences the system. In some systems,
the system boundaries are evident, e.g., for a tank reactor, the walls
of the tank are the system boundaries, and the outer world influences
the system through the inlet and outlet.

To make a differential mass balance, one must also describe the interior
of the system. In the simplest case, the system is homogenous (perfectly
mixed).

These two steps lead to a basic description of the system and its
boundaries, which, in chemical engineering, is called a reactor model.
The three most simple reactor models are listed below:

-   Ideal (continuously stirred) batch reactor

-   Ideal tank reactor, also named continuously stirred tank reactor
    (CSTR)

-   Ideal plug flow reactor (PFR)

### Ideal Batch Reactor

The ideal batch reactor is a closed system. Many chemistry textbooks
implicitly assume that the studied system can be described as a batch
reactor when they write about reaction kinetics and chemical
equilibrium. The mass balance for a substance, A, becomes

IN + PROD = OUT + ACC

> ![](media/image2.png){width="1.7486111111111111in"
> height="0.4465277777777778in"}

where r~A~ denotes the rate at which substance A is produced, V is the
volume (which may be constant or not), and n~A~ is the number of moles
(n) of substance A.

In a fed-batch reactor, some reactants/ingredients are added
continuously or in pulses, whereas in a batch reactor, the
reactants/ingredients are added all at once. For this reason, mass
balances for fed-batch reactors are a bit more complicated.

Example: In this example, we will use the law of mass action to derive
the expression for a chemical equilibrium constant.

Assume we have a closed reactor in which the following liquid phase
reversible reaction occurs:

![](media/image3.png){width="1.8444444444444446in"
height="0.18888888888888888in"}

The mass balance for substance A becomes

IN + PROD = OUT + ACC

![](media/image2.png){width="1.7486111111111111in"
height="0.4465277777777778in"}

As we have a liquid phase reaction, we can (usually) assume a constant
volume, and since\
n~A~ = V \* C~A~, we get

![](media/image4.png){width="1.229861111111111in"
height="0.4465277777777778in"}

or

![](media/image5.png){width="0.9166666666666666in"
height="0.4479166666666667in"}

In many text books, this is given as the definition of reaction rate
without specifying the implicit assumption that we are talking about
reaction rate in a closed system with only one reaction. This is an
unfortunate mistake that has confused many students over the years.

According to the law of mass action, the forward reaction rate can be
written as

r~1~ = k~1~ \[A\]^a^\[B\]^b^

and the backward reaction rate as

r ~−\ 1~ = k ~−\ 1~1\[C\]^c^\[D\]^d^

The rate at which substance A is produced is thus

r~A~ = r ~−\ 1~ − r~1~

and since, at equilibrium, the concentration of A is constant, we get

![](media/image6.png){width="2.2916666666666665in"
height="0.4479166666666667in"}

or, rearranged

![](media/image7.png){width="1.9465277777777779in"
height="0.5423611111111111in"}

### Ideal Tank Reactor/Continuously Stirred Tank Reactor (CSTR)

The ideal tank reactor/CSTR is an open system. A lake can be regarded as
a tank reactor, and lakes with long turnover times (e.g., with a low
flux to volume ratio) can for many purposes be regarded as continuously
stirred (e.g., homogenous in all respects). The mass balance becomes

IN + PROD = OUT + ACC

![](media/image8.png){width="3.1979166666666665in"
height="0.4479166666666667in"}

where Q_0 and Q denote the volumetric flow in and out of the system
respectively, and C_A_0 and C_A denote the concentration of A in the
inflow and outflow respectively. In an open system, we can never reach a
chemical equilibrium. We can, however, reach a steady state where all
state variables (temperature, concentrations, etc.) remain constant (ACC
= 0).

Example: Consider a bathtub in which we have dissolved some bathing
salt. We now add more water, keeping the plug in the drain. What
happens?

Since there is no reaction, PROD = 0, and since there is no outflow, Q =
0. The mass balance becomes

IN + PROD = OUT + ACC

![](media/image9.png){width="2.6770833333333335in"
height="0.4479166666666667in"}

or

![](media/image10.png){width="3.3645833333333335in"
height="0.4479166666666667in"}

Using a mass balance for total volume, however, it is evident that
![](media/image11.png){width="0.8333333333333334in"
height="0.4465277777777778in"} and that\
V = Vt ~=\ 0~ + Q~0~t. Thus we get

![](media/image12.png){width="2.9166666666666665in" height="0.5in"}

Note that there is no reaction, and hence no reaction rate or rate law
involved, and yet ![](media/image13.png){width="0.8020833333333334in"
height="0.4479166666666667in"}. We can thus draw the conclusion that
reaction rate cannot be defined in a general manner using
![](media/image14.png){width="0.3333333333333333in"
height="0.4479166666666667in"}. One must first write down a mass balance
before a link between
![](media/image14.png){width="0.3333333333333333in"
height="0.4479166666666667in"} and the reaction rate can be found. Many
textbooks, however, define reaction rate as

![](media/image15.png){width="0.8125in" height="0.4479166666666667in"}

without mentioning that this definition implicitly assumes (1) that the
system is closed,\
(2) that it has constant volume, and (3) that there is only one
reaction.

### Ideal Plug Flow Reactor (PFR)

An ideal PFR is an open system with no mixing along the reactor, but
perfect mixing across the reactor. It is often used for systems like
rivers and water pipes if the flow is turbulent. When a mass balance is
made for a tube, one must first consider an infinitesimal part of the
tube and make a mass balance over it using the ideal tank reactor model.
That mass balance is then integrated over the entire reactor volume. In
numeric solutions, e.g., when using computers, the ideal tube is often
translated to a series of tank reactors.

#### More complex problems. In reality, while reactors are often non-ideal, combinations of the reactor models addressed above are used to describe their systems. Not only chemical reaction rates, but also mass transfer rates, may be important in the mathematical description of a system, especially in heterogeneous systems.

As the chemical reaction rate depends on temperature, it is often
necessary to make an energy balance (often a heat balance rather than a
full-fledged energy balance) as well as mass balances to fully describe
the system. A different reactor model might be needed for the energy
balance. A system that is closed with respect to mass might be open with
respect to energy, since heat may enter the system through conduction.

c)  Define the following mass transfer terms and vapor-liquid
    equilibrium laws:

-   Absorption

-   Adsorption

-   Partition coefficient

-   Raoult's law

-   Dalton's law

-   Henry's law

-   Azeotropes

-   Phase diagrams

-   Vapor-liquid equilibrium

-   Binary phase equilibria

-   Multi-component vapor equilibria

-   Bubble-point, dew point, relative volatility

### Absorption

Absorption is the taking of molecules of one substance directly into
another substance. Absorption may be either a physical or a chemical
process. Physical absorption involves such factors as solubility and
vapor-pressure relationships, and chemical absorption involves chemical
reactions between the absorbed substance and the absorbing medium.
Absorption is a different process from adsorption, since the molecules
are taken up by the volume, and not by surface. A more general term is
sorption, which covers adsorption, absorption, and ion exchange.

If absorption is a physical process not accompanied by any other
physical or chemical process, it usually follows the Nernst partition
law: "The ratio of concentrations of some solute species in two bulk
phases in contact is constant for a given solute and bulk phases,"

![](media/image16.png){width="1.6256944444444446in"
height="0.35694444444444445in"}.

The value of constant K~N~ depends on temperature, and is called the
partition coefficient. This equation is valid if concentrations are not
too large, and if the species "x" does not change its form in any of the
two phases ("1" or "2"). If such molecule undergoes association or
dissociation, then this equation still describes the equilibrium between
"x" in both phases, but only for the same form. Concentrations of all
remaining forms must be calculated by taking into account all the other
equilibria.

In the case of gas absorption, one may calculate its concentration by
using the Ideal gas law, c = p/RT. Alternatively, one may use partial
pressures instead of concentrations.

In many technologically important processes, chemical absorption is used
in place of the physical process, e.g., absorption of carbon dioxide by
sodium hydroxide. Such processes do not follow the Nernst partition law.

The above information was taken from
[http://en.wikipedia.org/wiki/Absorption\_%28chemistry%29](http://en.wikipedia.org/wiki/Absorption_(chemistry))[.]{.underline}

### Adsorption

Adsorption is a chemical process that takes place when a liquid or, more
commonly, a gas (adsorbate) accumulates on the surface of a solid
(adsorbent), forming a molecular or atomic film.

Adsorption, similar to surface tension, is a consequence of surface
energy. Consider a clean surface exposed to a gaseous atmosphere. In the
bulk material, all the bonding requirements (be they ionic, covalent, or
metallic) of the constituent atoms of the material are filled. However,
atoms on the surface experience a bond deficiency because they are not
wholly surrounded by other atoms. It is then energetically favorable for
these dangling bonds to react with whatever happens to be available. The
exact nature of the bonding depends on the details of the species
involved, but the adsorbed material is generally classed as
experimenting physisorption or chemisorption.

### Partition Coefficient

LogP is a measure of the differential solubility of a compound in two
solvents. The log ratio of the concentrations of the solute in the
solvent is called LogP, or the partition coefficient. The best known of
these partition coefficients is the one based on the solvents octanol
and water. The octanol-water partition coefficient is a measure of the
hydrophobicity and hydrophilicity of a substance. In the context of
drug-like substances, hydrophobicity is related to absorption,
bioavailability, hydrophobic drug-receptor interactions, metabolism, and
toxicity.

### Raoult's Law

In chemistry, Raoult's law states that the vapor pressure of each
component in an ideal solution is dependent on the vapor pressure of the
individual component and the mole fraction of the component present in
the solution.

Once the components have reached equilibrium in the solution, the total
vapor pressure of the solution is

> ![](media/image17.png){width="3.3833333333333333in"
> height="0.2604166666666667in"}

and the individual vapor pressure for each component is

> ![](media/image18.png){width="1.4069444444444446in"
> height="0.2604166666666667in"}

where:

(P~i~)~pure~ is the vapor pressure of the pure component

X~i~ is the mole fraction of the component in solution

Consequently, as the number of components in a solution increases, the
individual vapor pressures decrease, since the mole fraction of each
component decreases with each additional component. If a pure solute
that has zero vapor pressure (it will not evaporate) is dissolved in a
solvent, the vapor pressure of the final solution will be lower than
that of the pure solvent.

This law is strictly valid only under the assumption that the bonding
between the two liquids is equal to the bonding within the liquids (the
conditions of an ideal solution). Therefore, comparing actual measured
vapor pressures to predicted values from Raoult's law allows information
about the relative strength of bonding between liquids to be obtained.
If the measured value of vapor pressure is less than the predicted
value, fewer molecules have left the solution than expected. This is
attributed to the strength of bonding between the liquids being greater
than the bonding within the individual liquids, so fewer molecules have
enough energy to leave the solution. Conversely, if the vapor pressure
is greater than the predicted value, more molecules have left the
solution than expected due to the bonding between the liquids being less
strong than the bonding within each liquid.

### Dalton's Law

Dalton's law was stated by John Dalton in 1801. In chemistry and
physics, Dalton's law (also called Dalton's law of partial pressure) is
related to the gas laws. It states that the total pressure exerted by a
gaseous mixture is equal to the sum of the partial pressures of each
individual component in a gas mixture.

More precisely, the pressure, P, of a mixture of n gases can be defined
as the summation

> ![](media/image19.png){width="2.3125in"
> height="0.22777777777777777in"}

where *p~1~, p~2~, p~n~* represent the partial pressure of each
component.

It is assumed that the gases do not react with each other.

Dalton's law also states that each individual component in any gas
mixture exerts its own partial pressure in the exact ratio as its mole
fraction.

> ![](media/image20.png){width="1.1965277777777779in"
> height="0.20694444444444443in"}

where *m~i~* = the mole fraction of the ith component in the total
mixture of m components.

The relationship below provides a way to determine the volume-based
concentration of any individual gaseous component.

> ![](media/image21.png){width="1.4069444444444446in"
> height="0.5006944444444444in"}

where *C* ~i~ = the concentration of the ith component expressed in ppm.

Dalton's law is not exact for real gases at very high pressure. At high
pressure, the volume of the molecules can become significant compared to
the free space between them.

### Henry's Law

In chemistry, Henry's law is one of the gas laws. It states that, at
equilibrium, the mass of a gas that is dissolved in a definite volume of
liquid is directly proportional to the pressure of the gas, provided the
gas does not react with the solvent. William Henry first formulated the
law in 1801.

Henry's law states, "The amount of gas (the mass) absorbed by a liquid
is directly proportional to the partial pressure of that gas in contact
with the liquid and the solubility coefficient of the gas in the
particular liquid."

A formula for Henry's law is:

![](media/image22.png){width="0.8333333333333334in"
height="0.20694444444444443in"}

where:

P = the partial pressure of the gaseous solute above the solution

C = the concentration of the dissolved gas in mol/L

k = the Henry's law constant, which has units such as J/mol, L·atm/mol
or Pa·m\^3/mol

Taking the natural logarithm of the formula gives us the more commonly
used formula:

P = kC

This version is used to showcase the effectiveness of the law for dilute
solutions of gases that don't react with the solvent. Some values for k
include

-   O~2~: 4.34×10^4^ L·atm/mol

-   CO~2~: 1.64×10^3^ L·atm/mol

-   H~2~: 7.04×10^4^ L·atm/mol

when these gases are dissolved in water at 299 K. Note that the
solubility coefficient varies with solvent and temperature.

### Azeotropes

An azeotrope is a liquid mixture of two or more compounds (molecules)
that retains the same composition in the vapor state as it does in the
liquid state when it is distilled or partially evaporated under a
certain pressure. This means that you cannot change the composition of
that liquid at its azeotropic composition by simple boiling. This
constant composition will (almost always) occur at a minimum or maximum
temperature over the composition space. The exception for binary
mixtures is the rare double azeotrope. The exception for three or more
components is the intermediate boiling azeotrope (saddle azeotrope).

To enrich a mixture past the azeotrope, one may use several techniques:

-   Use azeotropic distillation by adding in a third component that will
    generate a lower boiling heterogeneous azeotrope that can be broken
    by phase-separating the two immiscible liquids and decanting.

-   Use extractive distillation where a third compound is added near the
    top of a distillation column that reduces the volatility of one
    compound over another.

-   Use liquid-liquid extraction to separate the compounds by
    segregating them into two different liquid phases.

-   Use a membrane to separate the compounds, as in pervaporation.

-   For azeotropes that change composition when pressure is changed, you
    can use pressure swing distillation by operating two distillation
    columns at different pressures, and recycle material between these
    two distillation columns. One column will remove a pure component
    (two-component systems) in the bottom of one distillation column,
    the other will remove a pure component in the bottom of a second
    distillation column, and the azeotrope (of two different
    compositions) will be fed to the other column.

The word azeotrope comes from the Greek "zein tropos," or "constant
boiling." An azeotrope is said to be positive if the constant boiling
point is at a temperature maximum and negative when the boiling point is
at a temperature minimum. The vast majority of azeotropes are minimum
boiling. All liquid mixtures which are immiscible and which form
azeotropes are minimum boiling.

### Phase Diagrams

In physical chemistry and materials science, a phase diagram is a type
of graph used to show the equilibrium conditions between the
thermodynamically distinct phases. In mathematics and physics, a phase
diagram also has an alternative meaning as a synonym for a phase space.

The simplest phase diagrams are pressure-temperature diagrams of a
single, simple substance, such as water. The axes correspond to the
pressure and temperature. The phase diagram shows, in
pressure-temperature space, the lines of equilibrium or phase boundaries
between the three phases of solid, liquid, and gas.

A typical phase diagram is shown below. The dotted line gives the
anomalous behavior of water. The markings on the phase diagram show the
points where the free energy is non-analytic. The open spaces, where the
free energy is analytic, correspond to the phases. The phases are
separated by lines of non-analyticity where phase transitions occur,
which are called phase boundaries.

![](media/image23.png){width="4.679861111111111in"
height="3.1284722222222223in"}

**Figure 1.** Phase diagram example

In the diagram, the phase boundary between liquid and gas does not
continue indefinitely. Instead, it terminates at a point on the phase
diagram called the critical point. This reflects the fact that, at
extremely high temperatures and pressures, the liquid and gaseous phases
become indistinguishable. In water, the critical point occurs at around
647 K (374°C or 705°F) and 22.064 megapascals (Mpa).

The existence of the liquid-gas critical point reveals a slight
ambiguity in the definitions. When going from the liquid to the gaseous
phase, one usually crosses the phase boundary, but it is possible to
choose a path that never crosses the boundary by going to the right of
the critical point. Thus, the liquid and gaseous phases can blend
continuously into each other. However, it is impossible for the
solid-liquid phase boundary to end in a critical point in the same way
as the liquid-gas boundary because the solid and liquid phases have
different symmetry.

The solid-liquid phase boundary in the phase diagram of most substances,
such as the one shown in figure 1, has a positive slope. This is due to
the solid phase having a higher density than the liquid so that
increasing the pressure increases the melting temperature. However, in
the phase diagram for water, the solid-liquid phase boundary has a
negative slope. This reflects the fact that ice has a lower density than
water, which is an unusual property for a material.

Other, more complex types of phase diagrams can be constructed. For
example, phase diagrams can involve substances that take on more than
just three states of matter. Also, phase diagrams can use other
variables in place of temperature and pressure. Phase diagrams with more
than two dimensions can be constructed that show the effect of more than
two variables on the phase of a substance.

One type of phase diagram plots temperature against the relative
concentrations of two substances in a binary mixture. Such a mixture can
be either a solid solution or a eutectic. These two types of mixtures
result in very different graphs. A textbook example of a eutectic phase
diagram is that of the olivine (forsterite and fayalite) system.

A complex phase diagram of great technological importance is that of the
iron-carbon system for less than 7 percent carbon.

Common components of a phase diagram. Lines of equilibrium or phase
boundaries refer to the lines that demarcate where phase transitions
occur.

A triple point in a pressure-temperature phase diagram is the unique
intersection of the lines of equilibrium between three states of matter,
usually solid, liquid, and gas.

For a phase diagram with temperature on the vertical axis, a solidus is
a line below which the substance is stable in the solid state. A
liquidus is a line above which the substance is stable in a liquid
state. There may be a gap between the solidus and liquidus; within the
gap, the substance is not stable as either a solid or a liquid.

### Vapor-Liquid Equilibrium

Vapor pressure is the pressure of a vapor in equilibrium with its
non-vapor phases. Most often the term is used to describe a liquid's
tendency to evaporate. At any given temperature, for a particular
substance, there is a pressure at which the vapor of that substance is
in equilibrium with its liquid or solid forms. This is the equilibrium
vapor pressure, or saturation vapor pressure, of that substance at that
temperature. The term vapor pressure is often understood to mean the
saturation vapor pressure. A substance with a high vapor pressure at
normal temperatures is often referred to as volatile. The higher the
vapor pressure of a material at a given temperature, the lower the
boiling point will be.

### Binary Phase Equilibria

Binary phase equilibria refers to the equilibrium state achieved in a
material system in which there are no chemical reactions taking place
between various species. Because of the absence of chemical reactions,
the amount of each species is conserved.

### Multi-Component Vapor Equilibria

Prediction of phase equilibrium for multicomponent systems containing
associating compounds (e.g., water and alcohols) is essential in a
number of engineering applications (e.g., environmental technology, gas
hydrate inhibition), and at the same time represents one of the most
stringent tests for a thermodynamic model. Conventional models (e.g.,
cubic equations of state and excess Gibbs free energy models) provide
rapid and often reliable estimates of phase equilibrium in many cases,
but extension to multicomponent systems, especially those containing
water, is often troublesome.

### Bubble-Point, Dew Point, Relative Volatility

The bubble-point is the temperature at which the liquid starts to boil.
The dew-point is the temperature at which the saturated vapor starts to
condense. Relative volatility is a measure of the differences in
volatility between two components, and hence their boiling points. It
indicates how easy or difficult a particular separation will be.

d)  Discuss how the vapor-liquid equilibrium laws may be applied to
    determine a composite lower flammability limit in a vessel vapor
    space.

A flammable liquid stored in a confined space evaporates at a rate that
depends on its temperature and on the amount of vapor that is already
present in the air space above the liquid. Over time, the amount of
evaporated vapor in that air space will stabilize at an equilibrium
level called the ambient saturation concentration. A liquid's ambient
saturation concentration reflects the magnitude of its vapor pressure
compared with the vapor pressure of the air above it. If a chemical has
a high ambient saturation concentration, it has a strong ability to
displace air, and the concentration of the chemical's vapor in the air
above the liquid will be high. If it has a low ambient saturation
concentration, the vapor concentration will be low. This property
changes with temperature. A liquid at a higher temperature will have a
higher ambient saturation concentration.

You can calculate the ambient saturation concentration at a given
temperature for any liquid if you have a value for the liquid's vapor
pressure at that temperature and a value for the atmospheric pressure at
the location. To do this, divide the vapor pressure by the atmospheric
pressure and then multiply the result by 100 to obtain a value for
ambient saturation concentration expressed as a percentage by volume.

You can use information from material safety data sheets (MSDS) to make
this calculation.

Example for p-xylene: Assume the temperature of p-xylene is close to the
temperature around it, about 70°F. You can calculate p-xylene's ambient
saturation concentration at that temperature because the MSDS provides a
value for p-xylene's vapor pressure at 70°F. That value is 6.98
millimeters of mercury (mmHg). Atmospheric pressure at sea level is
760 mmHg. So,

![](media/image24.png){width="4.1819444444444445in"
height="0.43472222222222223in"}

This value is lower than p-xylene's lower flammability limit of 1.1%,
indicating that while the temperature remains at about 70°F, the
p-xylene vapor in the vessel is expected to be too lean to burn or
explode.

But this ambient saturation concentration is only slightly lower than
the lower flammability limit. When faced with such a result, it is
important to remember that there is uncertainty in each of the factors
that go into this calculation. Neither the lower flammability limit nor
the vapor pressure is an absolute, exact value. Both values were
obtained by measuring samples of p-xylene in a laboratory under specific
conditions that would not be exactly duplicated in this example.
Likewise, the temperature around the vessel may not be exactly 70°F. If
the true lower flammability limit were actually a bit lower than 1.1%,
or the true temperature or vapor pressure a bit higher, the actual
ambient saturation concentration of the p-xylene vapor might lie within
the explosive range.

Consider what would occur if fire were to raise the temperature of the
p-xylene within the vessel. The temperature at which the ambient
saturation concentration of the stored p-xylene reaches the explosive
range roughly corresponds to the flash point. Like vapor pressure or
lower flammable limits, flash points are determined from laboratory
measurements. You can find an estimate of p-xylene's flash point in
MSDSs. This value, about 81°F, is displayed along with p-xylene's other
properties. If the temperature around the vessel were to exceed this
value, you should assume that the p-xylene vapor could catch fire or
explode if it were ignited.

e)  Perform an example calculation demonstrating the use of mass
    transfer coefficients to estimate a liquid to vapor mass transfer.

This is a performance-based competency. The qualifying official will
evaluate the completion of this competency.

## Chemical processing personnel shall demonstrate an expert-level knowledge of stoichiometry and reaction kinetics.

a)  Balance a chemical reaction equation and discuss the concepts of
    limiting reactant and theoretical product yield.

In chemistry, the limiting reactant, also called the reagent, is the
chemical that determines how far the reaction will go before the
chemical in question is used up, causing the reaction to stop. It is
determined by working out the balanced equation for the chemical
reaction, comparing how many units (moles) of each go into the reaction
(in a proportion), and then measuring how many moles of each chemical
will be used in that reaction. The chemical of which there are less
moles than the proportion requires is the limiting reactant. The
inherent problem with limiting reactants is that they are purely
theoretical. You can never actually prove that they exist. To calculate
the limiting reactant, you must consider the pressure and dipole
movements. If you can properly calculate the charge of the solutions,
you need not use balanced equations.

Example: Consider the balanced equation for the combustion of benzene.

![](media/image25.png){width="3.0in" height="0.20694444444444443in"}

If 1.5 moles of benzene are reacted with 7 moles of oxygen, the limiting
reactant can be determined by performing the calculations as explained
below.

Since 15 mol O~2~ reacts with 2 mol C~6~H~6~ (see balanced equation),
the number of moles of O~2~ that will react with 1.5 mol C~6~H~6~ is:

(1.5 mol C~6~H~6~) (15 mol O~2~/2 mol C~6~H~6~) = 11.25 mol O~2~

This means that 11.25 mol O~2~ is required to react with 1.5 mol
C~6~H~6~. Since only 7 mol O~2~ is present, the oxygen will be consumed
before benzene. Therefore, O~2~ must be the limiting reactant.

This conclusion can be verified by comparing the mole ratio of O~2~ and
C~6~H~6~ required by the balanced equation with the mole ratio actually
present:

> Required: mol O~2~/mol C~6~H~6~ = 15 mol O~2~/2 mol C~6~H~6~ = 7.5 mol
> O~2~
>
> Actual: mol O~2~/mol C~6~H~6~ = 7 mol O~2~/1.5 mol C~6~H~6~ = 4.7 mol
> O~2~

Since the actual ratio is too small, O~2~ is the limiting reagent.

In chemistry, theoretical yield is calculated assuming there is only one
reaction involved, all of the reactant is converted into product, and
all of the product is collected. It is the theoretical result of a
chemical reaction.

f)  Discuss how a rate constant for a first order reaction may be
    determined from experimental data.

In chemistry, a rate law is an equation that relates concentrations of
reactants to the reaction rate. The rate law can be used in a mass
balance to describe how the system changes. For simplicity, we here
assume that the system is a closed, homogeneous system with only one
reaction. For the reaction

![](media/image26.png){width="1.979861111111111in"
height="0.18888888888888888in"}

the rate law is

![](media/image27.png){width="1.3229166666666667in"
height="0.23958333333333334in"}

where *κ* is the reaction rate constant, and the exponents are reaction
orders. The reaction is of order *m* in A, and of order n in B. The
overall reaction order is m + n.

Usually, reaction orders are 0, 1, or 2, but they can be fractions or
even negative numbers.

A first-order reaction depends on the concentration of only one reactant
(a unimolecular reaction). Other reactants can be present, but each will
be zero-order. The rate law for a first-order reaction is

V = k \[A\]

where k is the first order rate constant that has units of 1/time.

If, and only if, this first-order reaction (1) occurs in a closed
system, (2) there is no net build-up of intermediates, and (3) there are
no other reactions occurring, it can be shown by solving a mass balance
for the system that

> ![](media/image28.png){width="1.1819444444444445in"
> height="0.4409722222222222in"}

The integrated first-order rate law is

> ![](media/image29.png){width="1.9048611111111111in"
> height="0.23958333333333334in"}

A plot of time t vs. --ln \[A\] gives a straight line with a slope equal
to the reaction rate constant. The half-life of a first-order reaction
can be determined using the equation

![](media/image30.png){width="0.7166666666666667in"
height="0.3923611111111111in"}

Emblematic of a first-order reaction is that all the half-lives are
equal.

Following are examples of first-order reactions:

> ![](media/image31.png){width="2.5229166666666667in"
> height="0.22777777777777777in"}
>
> ![](media/image32.png){width="2.7506944444444446in"
> height="0.23055555555555557in"}
>
> ![](media/image33.png){width="2.69375in"
> height="0.23680555555555555in"}

They are all first-order with respect to reactant.

g)  Discuss the effects of temperature, catalysts, agitation and other
    conditions upon a reaction rate.

The reaction rate for a reactant or product in a particular reaction is
defined as the amount (in moles or mass units) per unit time per unit
volume that is formed or removed. Knowledge of these rates is essential
in chemical engineering and environmental engineering.

For the reaction

![](media/image26.png){width="1.979861111111111in"
height="0.18888888888888888in"}

the formula reaction rate, r, is the rate at which a mole of substance A
reacts according to the reaction above. If we assume that (1) the system
is closed, (2) the reaction above is the only reaction, and (3) there is
no significant build-up of intermediates, we can relate the reaction
rate, r, to changes in concentrations as

![](media/image34.png){width="3.584722222222222in" height="0.4375in"}

where \[A\] and \[B\] represent the concentration of the reactants. If,
however, one or more of these assumptions are not valid, we need to use
a mass balance to relate r to changes in concentration. Evidently, the
formula reaction rate relates to the reaction rate for individual
substances. If the three assumptions above are valid, we simply get

*r* = − *ar~A~* = − *br~B~* = − *cr~C~* = − *dr~D~*

If we have more than one reaction, e.g., one reaction which consumes A
and one which produces A, we may write the total reaction rate for A as
the sum of contributions from the two different reactions:

r~A~ = a~1~r~1~ − a~2~r~2~

Reaction rate is often expressed in the units mol/Ls. With information
of reaction rates, a rate law for this reaction can be established.

There are several factors that affect the rate of reaction:

-   Temperature. Conducting a reaction at a higher temperature puts more
    energy into the system and increases the reaction rate. The
    influence of temperature is described by the Arrhenius equation,
    whose result is factored into the equation by k. As a rule of thumb,
    the reaction rate doubles for every 10°C increase in temperature.

-   Concentration. As reactant concentration increases, the frequency of
    collision increases, and so therefore does the frequency of
    collisions having sufficient energy to cause reaction.

-   Pressure. The rate of gaseous reactions usually increases with an
    increase in pressure. Increase in pressure, in fact, is equivalent
    to an increase in concentration of the gas.

-   Light. Light is a form of energy. It may affect the rate or even
    course of a reaction. For example, when methane reacts with chlorine
    in the dark, the reaction rate would be very low. It can be speeded
    up when the mixture is put under diffused light. In bright sunlight,
    the reaction is explosive.

-   Order. Clearly, the order of the reaction has a major effect on its
    rate. The order of a reaction is found experimentally, and for most
    basic reactions, is an integer value.

-   A catalyst. The presence of a catalyst increases the reaction rate
    in both the forward and reverse reactions by providing an
    alternative pathway with a lower activation energy.

-   The nature of the reactants. If a reaction involves the breaking and
    reforming of bonds (complex) compared to just the forming of bonds
    (simple), then it generally takes longer. The reactants position in
    the reactivity series also affects reaction rate.

-   Surface area. In a heterogeneous system, as the surface area
    increases, the rate of reaction increases. The larger the surface
    area compared to the volume, the faster a reaction can take place,
    as more simultaneous reactions can occur.

The above information was taken from
<http://en.wikipedia.org/wiki/Reaction_rate>[.]{.underline}

## Chemical processing personnel shall demonstrate an expert-level knowledge of process safety.

a)  Discuss key requirements of the Process Safety Management (PSM)
    Rule\
    (29 CFR 1910.119).

The following are key requirements of the PSM rule:

-   The employer should complete a compilation of written process safety
    information before conducting any process hazard analysis. The
    compilation of written process safety information is to enable the
    employer and the employees involved in operating the process to
    identify and understand the hazards posed by those processes
    involving highly hazardous chemicals. This process safety
    information should include information pertaining to the hazards of
    the highly hazardous chemicals used or produced by the process,
    information pertaining to the technology of the process, and
    information pertaining to the equipment in the process.

-   The employer should perform an initial process hazard analysis
    (hazard evaluation) on processes covered by 29 CFR 1910.119. The
    process hazard analysis should be appropriate to the complexity of
    the process and shall identify, evaluate, and control the hazards
    involved in the process. Employers should determine and document the
    priority order for conducting process hazard analyses based on a
    rationale that includes such considerations as extent of the process
    hazards, number of potentially affected employees, age of the
    process, and operating history of the process.

-   The employer should develop and implement written operating
    procedures that provide clear instructions for safely conducting
    activities involved in each covered process consistent with the
    process safety information.

-   Each employee presently involved in operating a process, and each
    employee before being involved in operating a newly assigned
    process, should be trained in an overview of the process and in the
    operating procedures as specified in paragraph (f) of 29 CFR
    1910.119. The training should include emphasis on the specific
    safety and health hazards, emergency operations including shutdown,
    and safe work practices applicable to the employee's job tasks.

-   The employer should perform a pre-startup safety review for new
    facilities and for modified facilities when the modification is
    significant enough to require a change in the process safety
    information.

-   The employer shall issue a hot work permit for hot work operations
    conducted on or near a covered process.

-   The employer should establish and implement written procedures to
    manage changes to process chemicals, technology, equipment, and
    procedures, and changes to facilities that affect a covered process.

-   The employer should investigate each incident that resulted in, or
    could reasonably have resulted in, a catastrophic release of highly
    hazardous chemicals in the workplace.

-   The employer should establish and implement an emergency action plan
    for the entire plant in accordance with the provisions of 29 CFR
    1910.38. In addition, the emergency action plan should include
    procedures for handling small releases. Employers covered under this
    standard may also be subject to the hazardous waste and emergency
    response provisions contained in 29 CFR 1910.120.

-   Employers should certify that they have evaluated compliance with
    the provisions of 29 CFR 1910.119 at least every three years to
    verify that the procedures and practices developed under the
    standard are adequate and are being followed.

-   Employers should make all information necessary to comply with 29
    CFR 1910.119 available to those persons responsible for compiling
    the process safety information, those assisting in the development
    of the process hazard analysis, those responsible for developing the
    operating procedures, and those involved in incident investigations,
    emergency planning and response, and compliance audits without
    regard to possible trade secret status of such information.

h)  Discuss the role of chemical processing personnel in performing
    process hazard analysis and other parts of PSM.

Chemical processing personnel should use one or more of the following
methodologies that are appropriate to determine and evaluate the hazards
of the process being analyzed.

-   What-If Analysis

-   Checklist Analysis

-   What-If/Checklist Analysis

-   Hazard and Operability Study (HAZOP)

-   Failure Mode and Effects Analysis (FMEA)

-   Fault Tree Analysis

-   An appropriate equivalent methodology

The process hazard analysis shall address the following:

-   The hazards of the process

-   The identification of any previous incident which had a likely
    potential for catastrophic consequences in the workplace

-   Engineering and administrative controls applicable to the hazards
    and their interrelationships, such as appropriate application of
    detection methodologies to provide early warning of releases
    (Acceptable detection methods might include process monitoring and
    control instrumentation with alarms, and detection hardware such as
    hydrocarbon sensors.)

-   Consequences of failure of engineering and administrative controls

-   Facility siting

-   Human factors

-   A qualitative evaluation of a range of the possible safety and
    health effects of failure of controls on employees in the workplace

The process hazard analysis should be performed by a team with expertise
in engineering and process operations, and the team should include at
least one employee who has experience and knowledge specific to the
process being evaluated. Also, one member of the team must be
knowledgeable in the specific process hazard analysis methodology being
used.

The employer should establish a system to promptly address the team's
findings and recommendations; assure that the recommendations are
resolved in a timely manner and that the resolution is documented;
document what actions are to be taken; develop a written schedule of
when these actions are to be completed and complete the actions as soon
as possible; and communicate the actions to operating, maintenance, and
other employees whose work assignments are in the process, and who may
be affected by the recommendations or actions.

At least every five (5) years after the completion of the initial
process hazard analysis, the process hazard analysis should be updated
and revalidated by a team to assure that the process hazard analysis is
consistent with the current process.

Employers should retain process hazards analyses and updates or
revalidations for each process, as well as the documented resolution of
recommendations, for the life of the process.

i)  Discuss the following attributes of a personnel protection program:

-   MSDS and 29 CFR 1910.1200

-   Personal protective equipment (PPE)

### MSDS and 29 CFR 1910.1200

Employers should maintain copies of any MSDSs that are received with
incoming shipments of sealed containers of hazardous chemicals, should
obtain an MSDS as soon as possible for sealed containers of hazardous
chemicals that are received without an MSDS if an employee requests the
MSDS, and should ensure that the MSDSs are readily accessible during
each work shift to employees when they are in their work area.

### Personal Protective Equipment

When engineering and/or administrative controls have been considered and
implemented and are not sufficient to fully protect the worker from a
recognized hazard, PPE can be used to supplement these other controls as
appropriate. PPE is acceptable as a control method

-   to supplement engineering, work practice, and administrative
    controls when such controls are not feasible or do not adequately
    reduce the hazard;

-   as an interim measure while engineering controls are being developed
    and implemented;

-   during emergencies when engineering controls may not be feasible;

-   during maintenance and other non-routine activities where other
    controls are not feasible.

The use of PPE can itself create significant worker hazards, such as
heat stress, physical and psychological stress, and impaired vision,
mobility, and communication. An example would be a worker wearing
several layers of clothing (for warmth and anti-contamination), a
respirator, gloves, and a helmet while welding or cutting. This
arrangement of PPE could prevent the worker from being aware of the
environment in the event of a fire (for example, because of the lower
heat transfer rate) or other emergency.

In these situations, engineering and/or administrative controls (e.g., a
fire watch to ensure the safety of the worker as well as the property)
should be implemented to supplement PPE. Equipment and clothing should
be selected that provide an adequate level of protection. The selection
process should involve representatives of the affected safety
disciplines (e.g., health physicist, industrial hygienist, fire
protection staff) working in concert.

Two basic objectives of any PPE practice should be to protect the wearer
from safety and health hazards, and to prevent injury to the wearer from
incorrect use and/or malfunction of the PPE. To accomplish these
objectives, a comprehensive PPE practice should include hazard
identification (hazards that PPE will protect against and hazards caused
by the use of PPE), medical monitoring, environmental surveillance, and
selection, use, maintenance, and decontamination of PPE and its
associated training.

j)  Discuss the startup/re-start requirements of DOE O 425.1C.

Department of Energy (DOE) line management must determine (and ensure
that contractor management determines) if operational readiness reviews
(ORRs) are required for startup or restart of nuclear facilities using
the requirements given below. DOE must conduct (and ensure that
contractors conduct) an ORR in accordance with DOE O 425.1C when any of
the following conditions occur:

-   Initial startup of a new hazard category 1, 2, or 3 nuclear facility

-   Restart after a DOE management official directs the unplanned
    shutdown of a nuclear facility for safety or other appropriate
    reasons

-   Restart after an extended shutdown for hazard category 1 and 2
    nuclear facilities (An extended shutdown for a hazard category 1
    nuclear facility is 6 months. An extended shutdown for a hazard
    category 2 nuclear facility is 12 months.)

-   Restart of hazard category 1 and 2 nuclear facilities after
    substantial process, system, or facility modifications (The restart
    authority must determine if the modifications are substantial based
    on the impact of the changes on the safety basis and the extent and
    complexity of changes. This would not necessarily be determined by
    the unreviewed safety question \[USQ\] process.)

-   Restart after a nuclear facility shutdown because of operations
    outside the safety basis

-   When deemed appropriate by DOE management officials, including
    restarts of hazard category 3 nuclear facilities

For restarts of nuclear facilities not requiring an ORR, as defined in
DOE O 425.1C, DOE line management must evaluate (and ensure that
contractor management evaluates) the need for performing a readiness
assessment prior to restart. This includes the startup or restart of
program work associated with operating facilities when the new or
restarted program work does not require DOE approval of changes to
facility limits or requirements as stated in operational safety
requirements/technical safety requirements (OSRs/TSRs), basis for
interim operations/documented safety analysis (BIOs/DSAs), or other
equivalent authorization basis documents. When a readiness assessment is
required, operations offices must develop procedures and ensure that the
contractors use these procedures to gain operations office approval of
the startup or restart of nuclear facilities. If a readiness assessment
is not to be performed, the contractor's standard operating procedures
for startup or restart will be used.

k)  Discuss factors affecting integrity and performance of systems (age,
    pressure, service cycles, etc).

Age, pressure, service cycles, and other factors all affect the
integrity and performance of systems. Trends in system performance
should be monitored so as to be able to determine if significant
degradation of system performance is occurring over time. Such
degradation would justify revising the inspection, testing, and
maintenance program to feature more conservative frequencies.

l)  Discuss sources of information for chemical reactivity hazards, for
    lessons learned, and for historical records of nuclear and chemical
    industry accidents.

Chemical reactivity hazards present serious and sometimes catastrophic
danger to workers when the hazard is not thoroughly understood and
controlled. Hazardous releases have resulted in fires, explosions, and
toxic and/or high-energy events when chemical reactions have gone
astray. Conducting safe chemical reactions is key to the chemical
manufacturing industry and vitally important to employee health and
safety. The following references aid in recognizing chemical reactivity
hazards.

-   Essential Practices for Managing Chemical Reactivity Hazards,
    American Institute of Chemical Engineers (AIChE), Center for
    Chemical Process Safety (CCPS), 2003. This resource can help
    contribute to a continued reduction in the number and severity of
    incidents involving uncontrolled chemical reactions in the
    workplace. Free on-line access is now available.

-   Occupational Safety and Health Administration's (OSHA's) Thinking on
    Addressing Reactive Chemical Process Safety, a speech by John
    Henshaw, OSHA, September 23, 2003. This speech describes OSHA's
    strategy to reduce the number and severity of incidents involving
    chemical reactivity hazards.

-   PSM of Highly Hazardous Chemicals, OSHA Fact Sheet, 2002. This fact
    sheet discusses OSHA standard 29 CFR 1910.119, including its
    content, why it is necessary, and what industries are covered by the
    standard.

-   Reactive Material Hazards --- What You Need to Know, American
    Institute of Chemical Engineers (AIChE), Center for Chemical Process
    Safety (CCPS) Safety Alert, October 1, 2001. This resource presents
    an introduction to reactive material handling issues for people
    whose main business is not reactive materials and systems.

-   Chemicals Hazard Management at Exxon Mobil: Joint DOE/Energy
    Facility Contractors Group (EFCOG) Chemical Management 2001
    Workshop, Rick Vaughn, Exxon Mobil Research & Engineering Co.,
    October 23, 2001.

-   Chemical Accidents from Electric Power Outages, Environmental
    Protection Agency (EPA), Chemical Emergency Preparedness and
    Prevention Office (CEPPO) Chemical Safety Alert EPA 550-F-01-010,
    September 2001. This resource discusses how power outages and
    restarts could potentially trigger a serious chemical accident.

-   Process Safety Management, OSHA Publication 3132, 2000. This
    publication summarizes the OSHA final process safety management
    (PSM) standard, which applies to manufacturing industries, including
    those pertaining to chemicals, transportation equipment, and
    fabricated metal products.

-   Use Multiple Data Sources for Safer Emergency, Environmental
    Protection Agency (EPA), Chemical Emergency Preparedness and
    Prevention Office (CEPPO) Chemical Safety Alert, June 1999. This
    resource states that a critical consideration when choosing a
    response strategy is the safety of emergency responders. Adequate
    information about on-site chemicals can make a difference when
    choosing a safe response strategy.

-   Bretherick's Handbook of Reactive Chemical Hazards, 6th ed. Urben,
    P.G., ed., St. Louis: Elsevier Science and Technology Books, 2000.
    This handbook includes every chemical for which documented
    information on reactive hazards has been identified. It covers more
    than 5,000 elements and compounds, along with secondary entries
    involving two or more compounds, and features extensive
    cross-referencing, which links similar compounds of incidents not
    obviously related.

-   Dangerously Reactive Liquids and Solids and Their Hazards, Canadian
    Centre for Occupational Health and Safety (CCOHS). This resource
    answers questions about properties and hazards of dangerously
    reactive chemicals.

-   Fire Hazard from Carbon Adsorption Deodorizing Systems,
    Environmental Protection Agency (EPA), Chemical Emergency
    Preparedness and Prevention Office (CEPPO) Chemical Safety Alert EPA
    550-F-97-002e, May 1997. This resource discusses how activated
    carbon systems used to adsorb vapors for control of offensive odors
    may pose a fire hazard when used for certain types of substances if
    proper procedures are not followed.

-   Water-Reactive Chemicals, Hazardous Materials Not Covered Under 29
    CFR 1910.119, OSHA Hazard Information Bulletin (HIB), 1996. This
    bulletin highlights a potentially serious hazard regarding materials
    not covered by the process safety management (PSM) standard, 29 CFR
    1910.119.

-   Safe Disposal of Vented Reacting Fluids, Health & Safety Executive
    (HSE) Contract Research Report No. 100/1996, 1996. This report
    discusses the subject of relief for runaway reactions.

-   Guidelines for Chemical Reactivity Evaluation and Application to
    Process Design, American Institute of Chemical Engineers (AIChE),
    Center for Chemical Process Safety (CCPS), 1995. This resource
    provides principles and strategies for the evaluation of chemical
    reactions, and for using this information in process design and
    management.

-   Guidelines for Safe Storage and Handling of Reactive Materials,
    American Institute of Chemical Engineers (AIChE), Center for
    Chemical Process Safety (CCPS), 1995. This resource offers
    guidelines that can significantly reduce the risk or mitigate the
    severity of accidents associated with storing and handling reactive
    materials.

-   Process Safety Management of Highly Hazardous Chemicals, OSHA Fact
    Sheet\
    93-45, 1993. This fact sheet provides a general description of
    OSHA's Process Safety Management (PSM) of Highly Hazardous Chemicals
    (HHCs) Standard,\
    29 CFR 1910.119.

-   Safety and Health Guide for the Chemical Industry, OSHA Publication
    3091, 1986.\
    This guide encourages chemical industry employers to review and
    strengthen overall safety precautions to guard against chemical
    disaster. It contains information about safety programs, lists of
    acutely toxic chemicals, and health measures to protect workers.

-   Reactive Chemicals, Mary Kay O'Connor Process Safety Center. This
    resource provides a list of technical publications, including
    abstracts.

-   Thematic Network on Hazard Assessment of Highly Reactive Systems
    (HarsNet). European Commission, Industrial and Materials
    Technologies Programme. Provides a forum for universities, research
    centers and industries to collaborate in the development and
    dissemination of fundamental knowledge to be used for hazard
    assessment, improving the global safety of the chemical industry.
    Helps introduce hazard assessment techniques for reactive chemicals
    into the normal working procedures for small and medium enterprises
    and provides a number of project tasks related to various aspects of
    chemical safety.

Historical records of nuclear and chemical industry accidents are
available at the following links:

-   <http://www.infoplease.com/ipa/A0001457.html>

-   Nuclear Criticality Safety Division of the American Nuclear Society,
    <http://ncsd.ans.org/site/white_papers/ncsd_accidents_r1.pdf>

-   <http://www.lutins.org/nukes.html>

m)  Demonstrate a knowledge of basic chemical incompatibilities and
    reactive chemistry.

Some chemicals should not be mixed together. In fact, some chemicals
should not even be stored near each other because of the possibility
that an accident could occur and the chemicals could react. Here are
some examples of mixtures to avoid:

-   Acids with cyanide salts or cyanide solution, which would generate
    highly toxic hydrogen cyanide gas

-   Acids with sulfide salts or sulfide solutions, which would generate
    highly toxic hydrogen sulfide gas

-   Acids with bleach, which would generate highly toxic chlorine gas

-   Oxidizing acids (e.g., nitric acid, perchloric acid) with
    combustible materials (e.g., paper, alcohols, other common
    solvents), which could result in fire

-   Solid oxidizers (e.g., permanganates, iodates, nitrates) with
    combustible materials (e.g., paper, alcohols, other common solvents)

Reactive chemistry hazards can result from any chemical reaction with
the potential to release heat, pressure, or toxic reaction products in
quantities too high to be absorbed or contained by the environment and
equipment that holds the reacting mixture. It is important to
distinguish between reactive chemicals and hazardous chemical reactions.
The chemical substances in the process might not be considered to be
reactive chemicals, but this does not mean that the process does not
have reactivity hazards. Interactions of chemical substances may be more
important for understanding process hazards than the reactivity of
individual chemicals. Runaway reactions can occur from interactions
among chemicals not considered particularly reactive by themselves.

n)  Discuss TBP properties and hazards including decomposition products
    and "red oil" safety issues.

Tributyl phosphate (TBP), n-tributyl phosphate, or tri-n-butyl
phosphate, is an odorless liquid, colorless to pale yellow in
appearance, with applications in industrial and nuclear chemistry. It is
slightly flammable and moderately dangerous to humans. It is an ester of
orthophosphoric acid and n-butanol and is a very good solvent.

The material will burn, but in the absence of significant vaporization,
should not pose a particular explosive hazard. Inhalation and ingestion
should be avoided due to possible central nervous system effects. A lab
coat and safety glasses should be worn when working with TBP. While TBP
is not presently known to be, or suspected of being, a carcinogen, it
may be mutagenic or have reproductive effects. Consult the substance's
MSDS for additional information.

When in contact with concentrated nitric acid, the TBP-kerosene solution
forms hazardous and explosive red oil.

A 15%--40% (usually about 30%) solution of TBP in kerosene or dodecane
is used in the liquid-liquid extraction (solvent extraction) of uranium,
plutonium, and thorium from spent uranium nuclear fuel rods dissolved in
nitric acid as part of a nuclear reprocessing process known as PUREX.

Because of this, the shipment of 20 tons of TBP to North Korea from
China in 2002, coinciding with the resumption of activity at the
Yongbyon nuclear facilities, was seen by the United States and the
International Atomic Energy Agency as cause for concern. That amount of
TBP was considered sufficient to extract enough material for perhaps
three to five potential nuclear weapons.

Red oil is defined as a substance of varying composition formed when an
organic solution, typically TBP and its diluent, comes in contact with
concentrated nitric acid at a temperature above 120°C.

Red oil is relatively stable below 130°C, but it can decompose
explosively when its temperature is raised above 130°C. Three red oil
events have occurred in the United States: at the Hanford Site in 1953,
and at the Savannah River Site (SRS) in 1953 and 1975. A red oil
explosion also occurred in 1993 at the Tomsk-7 site in Seversk, Russia.

Generic types of equipment capable of producing red oil in the complex
are categorized as evaporators, acid concentrators, and denitrators. The
chemicals necessary to produce red oil are, at a minimum, TBP and nitric
acid; other contributory chemicals can include diluent (kerosene-like
liquid used to dilute TBP) and/or aqueous phase metal nitrates.

Controls for prevention or mitigation of a red oil explosion are
generally categorized as controls for temperature, pressure, mass, and
concentration. Maintaining a temperature of less than 130°C is generally
accepted as a means to prevent red oil explosions. Sufficient venting
serves to keep pressure from destroying the process vessel, while also
providing the means for evaporative cooling to keep red oil from
reaching the runaway temperature. Mass controls utilize decanters or
hydrocyclones to remove organics from feedstreams entering process
equipment capable of producing red oil. Limiting the total available TBP
is another mass control that mitigates the consequence of a red oil
explosion by limiting its maximum available explosive energy. Finally,
concentration control can be utilized to keep the nitric acid below 10 M
(moles/liter). A U.S. Government study concluded that none of the
controls should be used alone; rather, they should be used together to
provide effective defense in depth for prevention of a red oil
explosion.

## Chemical processing personnel shall demonstrate a working-level knowledge of DOE Safety Basis requirements.

a)  Discuss the following aspects of 10 CFR 830, subpart B:

-   Documented Safety Analyses (DSAs)

-   Technical Safety Requirements (TSRs)

-   Unreviewed Safety Question (USQ)

-   Safe Harbor Methodology

-   DOE-STD 1027, Hazard Categorization and Accident Analysis Techniques
    for Compliance with DOE Order 5480.23, Nuclear Safety Analysis
    Reports

-   DOE-STD 3009, Preparation Guide for U.S. Department of Energy
    Nonreactor Nuclear Facility Documented Safety Analyses

### Document Safety Analyses (DSAs)

Development of a DSA or preliminary documented safety analysis (PDSA) is
the process whereby facility hazards are identified, controls to prevent
and mitigate potential accidents involving those hazards are proposed,
and commitments are made for design, construction, operation, and
disposition so as to ensure adequate safety at DOE nuclear facilities.

### Technical Safety Requirements (TSRs)

TSRs define the performance requirements of structures, systems, and
components (SSCs) and identify the safety management programs used by
personnel to ensure safety. TSRs are aimed at confirming the ability of
the SSCs and personnel to perform their intended safety functions under
normal, abnormal, and accident conditions. These requirements are
identified through hazard analysis of the activities to be performed and
identification of the potential sources of safety issues. Safety
analyses to identify and analyze a set of bounding accidents that take
into account all potential causes of releases of radioactivity also
contribute to development of TSRs.

### Unreviewed Safety Question (USQ)

The purpose of the USQ process is to alert DOE of events, conditions, or
actions that affect the DOE-approved safety basis of the facility or
operation and ensure appropriate DOE line management action. If a change
is proposed or a condition is discovered that could increase the risk of
operating a facility beyond that established in the current safety
basis, DOE line management, including, where applicable, the NNSA, must
review and determine the acceptability of that risk through the process
of approving a revised safety basis that would be developed and
submitted by the contractor.

### Safe Harbor Methodology

Safe harbor methodologies are methodologies for DSA development that
have already been approved by DOE for use in specific circumstances.
Table 2 of appendix A to subpart B of 10 CFR 830 identifies the list of
safe harbor methodologies. Any other methods not listed in this table
require DOE approval before they can be used.

### DOE-STD-1027, Hazard Categorization and Accident Analysis Techniques for Compliance with DOE Order 5480.23, Nuclear Safety Analysis Reports

The purpose of DOE-STD-1027 is to establish guidance for the preparation
and review of hazard categorization and accident analyses techniques.
This DOE standard imposes no new requirements on nuclear facilities.
Instead, it focuses on (1) the definition of the standard identifying
nuclear facilities required to have DSAs, (2) the DSA implementation
plan and schedule, (3) the hazard categorization methodology to be
applied to all facilities, and (4) the accident analysis techniques
appropriate for the graded approach.

### DOE-STD-3009, Preparation Guide for U.S. Department of Energy Nonreactor Nuclear Facility Documented Safety Analyses

DOE-STD-3009 describes a DSA preparation method that is acceptable to
the DOE as delineated for those specific facilities listed in table 2 of
appendix A, "General Statement of Safety Basis Policy," to subpart B,
"Safety Basis Requirements," of 10 CFR 830. It was developed to assist
hazard category 2 and 3 facilities in preparing DSAs that will satisfy
the requirements of 10 CFR 830. Hazard category 1 facilities are
typically expected to be category A reactors for which extensive
precedents for DSAs already exist.

o)  Discuss the function of the following documents which may be in a
    Safety Basis Program:

-   Justification for Continued Operation

-   Basis for Interim Operations (DOE-STD 3011)

-   Potential Inadequacy in the Safety Analysis

-   New Information

-   Health and Safety Plan

-   Authorization Agreements

-   Criticality Safety Evaluation and the Double Contingency Principle\
    (DOE Order 420.1)

### Justification for Continued Operation

### A justification for continued operation is a document requesting DOE's approval of operation on a temporary basis after identifying a potential inadequacy of the safety analysis (PISA), a USQ, or some other condition in which the current safety basis requirements cannot be fully met or do not address the identified concern.

### Basis for Interim Operations (DOE-STD-3011)

### Traditionally, DSAs have been used as the long-term safety basis document for nuclear facilities usually under steady-sate conditions. There are primarily two cases where the rule allows a basis for interim operations (BIO) to be used as the appropriate safety basis documentation: (1) for short-lived activities, and (2) during transition phases, including transition surveillance and maintenance, deactivation, and decontamination and decommissioning. A BIO is applicable to a nuclear facility in transition as the facility moves through the appropriate life-cycle states, providing accurate safety documentation for rapidly changing activities. A BIO can also be linked to a series of tasks or activities. 

### Potential Inadequacy in the Safety Analysis

Written USQ determinations are required when a contractor identifies a
potential inadequacy of the safety analyses that support the
DOE-approved safety basis, which indicates the safety analysis is not
bounding or may be otherwise inadequate. The intent is to ensure that
the operations are conducted in a safe manner that is consistent with
the safety basis. Because an inadequacy in the safety analyses has the
potential to call into question information relied on for authorization
of operations, DOE requires the contractor to

-   take appropriate action to place or maintain the facility in a safe
    condition;

-   expeditiously notify DOE when the information is discovered;

-   perform a USQ determination and submit the results promptly;

-   complete an evaluation of the safety of the situation and submit it
    to DOE before removing any operational restrictions implemented to
    compensate for the analytical discrepancy.

### New Information

The DSA may be inadequate for any number of reasons. In general, it is
possible for a potentially inadequate analysis to arise from three entry
conditions: (1) a discrepant as-found condition, (2) an operational
event or incident, or (3) new information, including discovery or an
error, sometimes from an external source. The main consideration is that
the analysis does not match the current physical configuration of the
facility, or the analysis is inappropriate or contains errors.

### Health and Safety Plan

In the 1986 amendments to the Comprehensive Environmental Response,
Compensation, and Liability Act (CERCLA), Congress tasked the
Administrators of the EPA and OSHA, the Secretary of the Department of
Transportation (DOT), and the Director of the National Institute for
Occupational Safety and Health (NIOSH) to modify the National
Contingency Plan (NCP) (40 CFR 300) to provide for protection of health
and safety of employees involved in response actions. To satisfy this
directive, standards requiring the development of a site-specific health
and safety plan (HASP) were established by OSHA in 29 CFR 1910.120,
Hazardous Waste Operations and Emergency Response (HAZWOPER), and
incorporated into the NCP (40 CFR 300.150). Additionally, the NCP
requires compliance with standards and regulations of the Occupational
Safety and Health Act, including such standards as Construction Safety
(29 CFR 1926) and General Industry Standards (29 CFR 1910), where
applicable.

### Authorization Agreements

An authorization agreement is a documented agreement between DOE and the
contractor for a high-hazard facility (category 1 or 2), incorporating
the results of DOE's review of the contractor's proposed authorization
basis for a defined scope of work. The authorization agreement contains
key terms and conditions (controls and commitments) under which the
contractor is authorized to perform work. Any changes to these terms and
conditions require DOE approval.

### Criticality Safety Evaluation and the Double Contingency Principle (DOE Order 420.1)

A criticality safety evaluation is an evaluation developed for
fissionable materials operations that documents parameters, limits, and
controls that are required to maintain sub-criticality for all normal
and credible abnormal conditions.

Following the double contingency principle, process designs shall
incorporate sufficient factors of safety to require at least two
unlikely, independent, and concurrent changes in process conditions
before a criticality accident is possible. Protection shall be provided
by either (1) the control of at least two independent process
parameters, which is the approach that is completely consistent with the
double contingency principle as stated in ANSI/ANS-8.1-1998 and which,
when practical, is the approach preferred by DOE to be taken to prevent
common-mode failure, or (2) a system of multiple controls on a single
process (nuclear) parameter, which shall be the alternative approach to
be taken only when the preferred approach is shown to be impractical.

The number of controls required upon a single controlled process
parameter shall be based on control reliability and any features that
mitigate the consequences of control failure. In all cases, no single
credible event or failure shall result in the potential for a
criticality accident, except where single contingency operations are
permissible, as presented in paragraph 5.1 of ANSI/ANS-8.10-1983, R88.
This exception applies to operations with shielding and confinement
(e.g., hot cells or other shielded facilities). Double contingency shall
be demonstrated by documented evaluations.

## Chemical processing personnel shall demonstrate a working-level knowledge of safety and relief devices.

a)  Define the following terms as they pertain to safety and relief
    valves:

-   Set point

-   Accumulation

-   Blowdown

-   Weep

-   Pilot-actuated

-   Gagging device

### Set Point

For a safety valve, the set point is the setting that causes the valve
to pop open to relieve pressure. For relief valves, it is the point at
which the valve begins to open to relieve pressure. As pressure
decreases, the valve will reseat itself.

### Accumulation

Accumulation is the amount of fluid removed when a valve is operated
before it reseats.

### Blowdown

Blowdown is the pressure drop in a pressurized vessel from the opening
of a safety relief valve to the resetting of the valve.

### Weep

Weep is leakage past the seating surface while pressure is below the
set-point pressure.

### Pilot-Actuated

Pilot-actuated relief valves are designed to maintain pressure through
the use of a small passage to the top of a piston that is connected to
the stem such that system pressure closes the main relief valve. When
the small pilot valve opens, pressure is relieved from the piston, and
system pressure under the disc opens the main relief valve. Such pilot
valves are typically solenoid operated, with the energizing signal
originating from pressure measuring systems.

### Gagging Device

A gagging device is a device installed into relief valves to prevent
operation of the valves. Generally, they are only used during special
operations or maintenance.

p)  Compare and contrast the purpose and operation of safety and relief
    valves.

Safety and relief valves prevent equipment damage by relieving
accidental over-pressurization of fluid systems. The main difference
between a relief valve and a safety valve is the extent of opening at
the set-point pressure. A relief valve gradually opens as the inlet
pressure increases above the set point only as necessary to relieve the
over-pressure condition. A safety valve rapidly pops fully open as soon
as the pressure setting is reached. A safety valve will stay fully open
until the pressure drops below a reset pressure. The reset pressure is
lower than the actuating pressure set point. The difference between the
actuating pressure set point and the pressure at which the safety valve
resets is called blowdown. Relief valves are typically used for
incompressible fluids such as water or oil. Safety valves are typically
used for compressible fluids such as steam or other gases. Most relief
and safety valves open against the force of a compression spring. The
pressure set point is adjusted by turning the adjusting nuts on top of
the yoke to increase or decrease the spring compression.

q)  Discuss how blowdown and accumulation are controlled in safety and
    relief valves.

Blowdown and accumulation can be set by the manufacturer or with
adjustment screws on the valve. Different valves have different types of
adjustment requirements, and adjustments should be performed in
accordance with manufacturer recommendations.

r)  Using a cutaway drawing of a safety valve, identify the main
    components to include:

-   Seat

-   Disc

-   Blowdown ring

-   Main spring

-   Set-point adjustment mechanism

Note: This is a performance-based competency. The ability to complete
this competency must be observed by a qualifying official.

s)  Discuss the methods used to test relief valves.

There are two methods of testing relief valves: bench testing and
in-place testing. Bench testing requires you to remove the valve from
the system and test the valve on an authorized testing unit. In-place
testing uses a special test rig that you can purchase with the valve.

t)  Discuss the application of rupture discs.

Rupture discs are installed on vessels, piping, or valves to prevent
over-pressurization of these components. The rupture disc should fail
much sooner than any other component, thus minimizing any damage to the
system.

## Chemical processing personnel shall demonstrate working-level knowledge of general piping systems.

a)  Define the following terms as they relate to piping systems:

-   Pipe schedule

-   Water hammer

-   Hydrostatic test pressure

-   Laminar flow

-   Turbulent flow

### Pipe Schedule

The pipe schedule lists the pipe designs based on outside diameter,
nominal diameter, and wall thickness.

### Water Hammer

Water hammer is the result of a sudden change in liquid velocity. Water
hammer usually occurs when a transfer system is quickly started,
stopped, or forced to make a rapid change in direction.

### Hydrostatic Test Pressure

The fluid used for the hydrostatic test is typically water. Another
suitable non-toxic liquid can be substituted if there is the risk of
damage due to the adverse effects of having water in the system. The
system should be tested at a pressure not less than 1.5 times the design
pressure.

### Laminar Flow

Laminar flow is smooth and regular fluid flow, with the direction of
motion at any point remaining constant as if the fluid were moving in a
series of layers sliding over one another without mixing.

### Turbulent Flow

Turbulent flow is flow in which the flow lines are confused and the
fluid is heterogeneously mixed.

u)  Discuss the potential hazards to personnel and equipment associated
    with water hammer.

Water hammer can lead to catastrophic system component failure that
could injure workers or damage equipment.

v)  Identify and discuss the typical causes of water hammer in piping
    systems.

Water hammer usually occurs when a transfer system is quickly started,
stopped, or is forced to make a rapid change in direction. Without
question, the primary cause of water hammer in process applications is
the quick-closing valve, whether manual or automatic. A valve closing in
1.5 seconds or less, depending upon valve size and system conditions,
causes an abrupt stoppage of flow. The pressure spike (acoustic wave)
created at rapid valve closure can be as high as five times the system
working pressure.

w)  Discuss the purpose of seismic restraints (whip restraints or
    snubbers) in piping systems.

Suspended piping can move through large displacements in a seismic event
and damage surrounding building elements. It has been observed that the
pipe itself is very ductile and can withstand a great deal of bending
and shaking; however, piping connections to equipment can be easily
damaged in earthquakes. All seismic codes contain provisions for bracing
suspended piping for the purpose of life safety. Seismic bracing of
piping is not an option and is not left to the judgment of architects,
engineers, contractors, owners, or suppliers.

x)  Identify and discuss different methods of pipe joining (threaded,
    butt weld, socket weld, seal weld, etc.).

### Threaded

Pipes are threaded to allow them to be screwed together. Pipes that are
joined by threading can be used for low-pressure systems using materials
that are not hazardous.

### Butt Weld

A butt weld is made using a welding technique used to join two tubes in
which the squared and prepared ends are butted together in preparation
for welding. The resulting circumferential weld has relatively good
strength characteristics, but has limitations where the tube is to be
plastically deformed or bent, such as occurs on a coiled tubing string.
Consequently, butt welds performed on a coiled tubing string should be
checked carefully using hardness and radiographic testing methods, and
their locations should be detailed in the string record. The anticipated
fatigue life in the butt-weld area must also be reduced to compensate
for the weakness of the weld.

### Socket Weld

Socket welds are fittings used to allow pipes to be placed together in
ways that allow for different configurations. These configurations
consist of 90-degree elbows, crosses, tees, and pipe joints.

### Seal Weld

The purpose of a seal weld may be to contain a fluid --- either gaseous
or liquid. In the mechanical and structural fields, seal welds are used
most often not to prevent leakage out of a container, but to prevent
entry of a fluid into a space where some type of harmful behavior, often
corrosion, is expected to occur. In these fields, seal welds are
frequently used to preclude moisture and oxygen-laden air and water from
entering a cavity.

## Chemical processing personnel shall demonstrate a working-level knowledge of mechanical diagrams, including:

-   As-built drawings

-   Piping and Instrumentation Diagrams (P&ID)

a)  Using an engineering print, read and interpret the information
    contained in the title block, the notes and legend, the revision
    block, and the drawing grid.

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```
y)  Identify the symbols used in piping and instrumentation diagrams
    for:

-   Types of valves

-   Types of valve operators

-   Types of educators and ejectors

-   Basic types of instrumentation

-   Types of instrument signal controllers and modifiers

-   Types of system components (pumps, etc.)

-   Types of lines

z)  Identify the symbols used in piping and instrumentation diagrams to
    denote the location of instruments, indicators, and controllers.

a)  Identify how valve conditions are depicted.

b)  Determine system flowpath(s) for a given valve lineup.

c)  Discuss the origin and purpose of "as-built drawings."

Elements "a" through "f" are performance-based competencies. The
qualifying official will evaluate the completion of these competencies.

## Chemical processing personnel shall demonstrate a working-level knowledge of the general construction, operation, and theory of valves.

a)  Define the following terms as they relate to valves:

-   Disc

-   Seat

-   Throttle

-   Actuator

-   Bridgewall mark

-   Packing

### Disc

For a valve having a bonnet, the disc is the third primary principal
pressure boundary. The disc provides the capability to permit and
prohibit fluid flow. With the disc closed, full system pressure is
applied across the disc if the outlet side is depressurized. For this
reason, the disc is a pressure-retaining part. Discs are typically
forged, and in some designs, hard-surfaced to provide good wear
characteristics. A fine surface finish of the seating area of a disc is
necessary for good sealing when the valve is closed. Most valves are
named, in part, according to the design of their discs.

### Seat

The seat or seal rings provide the seating surface for the disc. In some
designs, the body is machined to serve as the seating surface, and seal
rings are not used. In other designs, forged seal rings are threaded or
welded to the body to provide the seating surface. To improve the
wear-resistance of the seal rings, the surface is often hard-faced by
welding and then machining the contact surface of the seal ring. A fine
surface finish of the seating area is necessary for good sealing when
the valve is closed. Seal rings are not usually considered pressure
boundary parts because the body has sufficient wall thickness to
withstand design pressure without relying upon the thickness of the seal
rings.

### Throttle

The term throttle indicates the ability to control flow. Some valves are
specifically made to perform this task; other valves demonstrate poor
characteristics in throttling or controlling flow in a valve.

### Actuator

Valve actuators are selected based upon a number of factors, including
torque necessary to operate the valve and the need for automatic
actuation. Types of actuators include manual hand-wheel, manual lever,
electrical motor, pneumatic, solenoid, hydraulic piston, and
self-actuated. All actuators except manual hand-wheel and lever are
adaptable to automatic actuation. These actuators will open, close, or
position the valve to a required position.

### Bridgewall Mark

A bridgewall mark on the side of a valve demonstrates how flow is
designed to go through the valve. It is used to show how the valve
should be installed.

### Packing

Most valves use some form of packing to prevent leakage from the space
between the stem and the bonnet. Packing is commonly a fibrous material
(such as flax) or another compound (such as Teflon) that forms a seal
between the internal parts of a valve and the outside where the stem
extends through the body. Valve packing must be properly compressed to
prevent fluid loss and damage to the valve's stem. If a valve's packing
is too loose, the valve will leak, which is a safety hazard. If the
packing is too tight, it will impair the movement and possibly damage
the stem.

d)  Using a drawing of a valve, identify which of the following general
    types of valve it is and, describe its normal design application in
    a piping system:

-   Gate

-   Globe

-   Ball

-   Check

-   Butterfly

-   Regulating/reducing

This is a performance-based competency. The qualifying official will
evaluate the completion of this competency.

e)  Discuss why the design of a globe valve enables it to throttle
    fluids efficiently.

The essential principle of globe valve operation is the perpendicular
movement of the disc away from the seat. This causes the annular space
between the disc and seat ring to gradually close as the valve is
closed. This characteristic gives the globe valve good throttling
ability, which permits its use in regulating flow.

f)  Using a diagram of a globe valve body showing the bridgewall mark,
    identify how the valve must be oriented in the system related to
    flow.

This is a performance-based competency. The qualifying official will
evaluate the completion of this competency.

g)  Discuss why gate valves, ball valves, and butterfly valves should
    never be used to throttle flow.

Because of the way gate valves, ball valves, and butterfly valves are
designed, throttling with these valves would cause severe seat erosion
and would lead to much quicker seating surface failure.

h)  Discuss how cavitation occurs in valves and state any harmful
    effects that can result from cavitation.

Fluids at higher temperatures that are throttled can lead to cavitation
in a valve. The pressure drop across the valve seat may lead to
instantaneous cavitation at the valve seat. The cavitation will cause
hardening of the surface, and as the surface hardens, it will become
more brittle and much more susceptible to breaking off and damaging the
seating surface.

i)  Describe the construction and principle of operation for the
    following types of valve actuators:

-   Manual

-   Electric

-   Solenoid

-   Pneumatic

-   Hydraulic

### Manual

Manual actuators are capable of placing the valve in any position, but
do not permit automatic operation. The most common type of mechanical
actuator is the handwheel. This type includes handwheels fixed to the
stem, hammer handwheels, and handwheels connected to the stem through
gears.

### Electric

Electric motors permit manual, semi-automatic, and automatic operation
of the valve. Motors are used mostly for open/close functions, although
they are adaptable for positioning the valve to any point. The motor is
usually a reversible, high-speed type connected through a gear train to
reduce the motor speed and thereby increase the torque at the stem.
Direction of motor rotation determines direction of disc motion. The
electrical actuation can be semi-automatic, as when the motor is started
by a control system. A handwheel, which can be engaged to the gear
train, provides for manual operating of the valve. Limit switches are
normally provided to stop the motor automatically at full-open and
full-closed valve positions. Limit switches are operated either
physically by position of the valve, or torsionally by torque of the
motor.

### Solenoid

Solenoid-actuated valves provide for automatic open/close valve
positioning. Most solenoid-actuated valves also have a manual override
that permits manual positioning of the valve for as long as the override
is manually positioned. Solenoids position the valve by attracting a
magnetic slug attached to the valve stem. In single solenoid valves,
spring pressure acts against the motion of the slug when power is
applied to the solenoid. These valves can be arranged such that power to
the solenoid either opens or closes the valve. When power to the
solenoid is removed, the spring returns the valve to the opposite
position. Two solenoids can be used to provide for both opening and
closing by applying power to the appropriate solenoid.

### Pneumatic

Pneumatic actuators provide for automatic or semiautomatic valve
operation. These actuators translate an air signal into valve stem
motion by air pressure acting on a diaphragm or piston connected to the
stem. Pneumatic actuators are used in throttle valves for open/close
positioning where fast action is required. When air pressure closes the
valve and spring action opens the valve, the actuator is termed
direct-acting. When air pressure opens the valve and spring action
closes the valve, the actuator is termed reverse-acting. Duplex
actuators have air supplied to both sides of the diaphragm. The
differential pressure across the diaphragm positions the valve stem.
Automatic operation is provided when the air signals are automatically
controlled by circuitry. Semi-automatic operation is provided by manual
switches in the circuitry to the air control valves.

### Hydraulic

Hydraulic actuators provide for semi-automatic or automatic positioning
of the valve, similar to the pneumatic actuators. These actuators use a
piston to convert a signal pressure into valve stem motion. Hydraulic
fluid is fed to either side of the piston while the other side is
drained or bled. Water or oil is used as the hydraulic fluid. Solenoid
valves are typically used for automatic control of the hydraulic fluid
to direct either opening or closing of the valve. Manual valves can also
be used for controlling the hydraulic fluid, thus providing
semi-automatic operation.

j)  Describe the principles of operation and applications for modulating
    and pressure reducing valves.

Reducing valves automatically reduce supply pressure to a preselected
pressure as long as the supply pressure is at least as high as the
selected pressure. The principal parts of the reducing valve are the
main valve, an upward-seating valve that has a piston on top of its
valve stem, an upward-seating auxiliary (or controlling) valve, a
controlling diaphragm, and an adjusting spring and screw. Reducing valve
operation is controlled by high pressure at the valve inlet and the
adjusting screw on top of the valve assembly. The pressure entering the
main valve assists the main valve spring in keeping the reducing valve
closed by pushing upward on the main valve disc. However, some of the
high pressure is bled to an auxiliary valve on top of the main valve.
The auxiliary valve controls the admission of high pressure to the
piston on top of the main valve. The piston has a larger surface area
than the main valve disc, resulting in a net downward force to open the
main valve. The auxiliary valve is controlled by a controlling diaphragm
located directly over the auxiliary valve.

## Chemical processing personnel shall demonstrate a working-level knowledge of measurement, data collection, and analysis.

a)  Discuss the types of instrumentation and the principles of operation
    for measuring chemical process parameters (e.g., pressure,
    temperature, flow) to include:

-   Resistance Temperature Detector (RTD)

-   Thermocouple

-   Differential pressure detector

-   Pitot tube

-   Bourdon tube pressure gauge

-   Duplex pressure gauge

-   Manometer

-   Mechanical flow meters

### Resistance Temperature Detector (RTD)

The RTD incorporates pure metals or certain alloys that increase in
resistance as temperature increases and, conversely, decrease in
resistance as temperature decreases. RTDs act somewhat like an
electrical transducer, converting changes in temperature to voltage
signals by the measurement of resistance. The metals that are best
suited for use as RTD sensors are pure, of uniform quality, stable
within a given range of temperature, and able to give reproducible
resistance-temperature readings. Only a few metals have the properties
necessary for use in RTD elements.

### Thermocouple

Thermocouples will cause an electric current to flow in the attached
circuit when subjected to changes in temperature. The amount of current
that will be produced is dependent on the temperature difference between
the measurement and reference junction, the characteristics of the two
metals used, and the characteristics of the attached circuit. Heating
the measuring junction of the thermocouple produces a voltage which is
greater than the voltage across the reference junction. The difference
between the two voltages is proportional to the difference in
temperature, and can be measured on a voltmeter. For ease of operator
use, some voltmeters are set up to read out directly in temperature
through use of electronic circuitry.

### Differential Pressure Detector

The differential pressure (P) detector method of liquid level
measurement uses a P detector connected to the bottom of the tank being
monitored. The higher pressure, caused by the fluid in the tank, is
compared to a lower reference pressure (usually atmospheric). This
comparison takes place in the P detector. The tank is open to the
atmosphere; therefore, it is necessary to use only the high-pressure
(HP) connection on the P transmitter. The low-pressure (LP) side is
vented to the atmosphere; therefore, the pressure differential is the
hydrostatic head, or weight, of the liquid in the tank. The maximum
level that can be measured by the P transmitter is determined by the
maximum height of liquid above the transmitter. The minimum level that
can be measured is determined by the point where the transmitter is
connected to the tank.

### Pitot Tube

The pitot tube is another primary flow element used to produce a
differential pressure for flow detection. In its simplest form, it
consists of a tube with an opening at the end. The small hole in the end
is positioned such that it faces the flowing fluid. The velocity of the
fluid at the opening of the tube decreases to zero. This provides for
the high-pressure input to a differential pressure detector. A pressure
tap provides the low-pressure input. The pitot tube actually measures
fluid velocity instead of fluid flow rate.

### Bourdon Tube Pressure Gauge

The bourdon tube pressure instrument is one of the oldest pressure
sensing instruments in use today. The bourdon tube consists of a
thin-walled tube that is flattened diametrically on opposite sides to
produce a cross-sectional area elliptical in shape, having two long,
flat sides and two short, round sides. The tube is bent lengthwise into
an arc of a circle of 270 to 300 degrees. Pressure applied to the inside
of the tube causes distention of the flat sections, and tends to restore
its original round cross-section. This change in cross-section causes
the tube to straighten slightly. Since the tube is permanently fastened
at one end, the tip of the tube traces a curve that is the result of the
change in angular position with respect to the center. Within limits,
the movement of the tip of the tube can then be used to position a
pointer.

### Duplex Pressure Gauge

A duplex pressure gauge is used to measure the absolute differential
pressure between two fluid systems or states, and can be used for any
gas or fluid.

### Manometer

Manometers measure a pressure difference by balancing the weight of a
fluid column between the two pressures of interest. Large pressure
differences are measured with heavy fluids, such as mercury. Small
pressure differences, such as those experienced in experimental wind
tunnels or venturi flowmeters, are measured by lighter fluids such as
water.

### Mechanical Flow Meters

There are several types of mechanical flow meters. These meters are
useful for a visual display of flow. There are more up-to-date methods
of measuring flow, but these are steady and constant with a long history
of use. In the basic operation of a mechanical flow meter, flow moves a
set mechanical piece of equipment which gives a reading that reflects
the actual flow.

k)  Discuss the following with respect to probability and statistics:

-   Standard deviation

-   Mean/median/mode

-   Variance

-   Sample size/frequency

-   Error analysis

### Standard Deviation

The standard deviation is the square root of variance. The formulas for
standard deviation are as follows:

Population or σ^2\ =^ $\sqrt{\frac{\sum_{}^{}(x - \mu)^{2}}{N}}$ or
Sample S^2^ =
$\sqrt{\frac{\sum_{}^{}\left( x - \overline{x} \right)^{2}}{N - 1}}$

Example:

The standard deviation for a group of children aged 5, 6, 8, and 9 is:

S = $\sqrt{S^{2}}$ =
$\sqrt{\frac{\sum_{}^{}\left( x - \overline{x} \right)^{2}}{N - 1}}$ =
$\sqrt{2\text{.}5}$ = 1.58

### Mean

The mean, in general terms, is the average value of the data set.

An average is a value that is typical or representative of a set of
data. The mean of a set of quantitative data is defined as the sum of
the measurements divided by the number of measurements contained in the
data set.

The arithmetic mean, or briefly the mean, of a set of N numbers X1, X2,
X3, ..., XN is denoted by X (read "X bar"), or the symbol m for a
population, and is defined as:

![](media/image35.png){width="3.2909722222222224in" height="0.65625in"}

Example:

For the data set 5 3 7 9 8 5 4 5 8, the mean is:

$\frac{7 + 3 + 5 + 8 + 8 + 5 + 4 + 5 + 9}{9}$ = $\frac{\text{54}}{9}$ =
6

### Median

The median of a set of numbers --- arranged in order of magnitude --- is
either the middle value for a data set with an odd number of members, or
the average of the two middle values if the data set contains an even
number of members.

Example:

  ----------------------------- ------------------- ---------------------
                                Odd-member set      Even-member set

  Data set                      7 3 5 9 7 5 4 5 9   2 3 6 4 2 7 2 7 9 8

  Order data set                3 4 5 5 **5** 7 7 9 2 2 2 3 **4 6** 7 7 8
                                9                   9

  Median                        5                   $\frac{4 + 6}{2}$ = 5
  ----------------------------- ------------------- ---------------------

### Mode

The mode of a set of numbers is that value which occurs with the
greatest frequency. The mode may not exist, and even if it does exist,
it may not be unique.

Examples:

  ----------------- ------------- --------------------- -----------------
                    Example 1     Example 2             Example 3

  Data set          3 4 **5 5 5** 3 5 8 10 12 15 16     2 3 **4 4 4** 5 5
                    7 8 8 9                             **7 7 7** 9

  Mode              5             No mode               4 and 7, bimodal
  ----------------- ------------- --------------------- -----------------

### Variance

One of the most commonly used measures of data variation is the
variance, which is termed s2 for a population and S2 for a sample. The
formulas are as follows:

Population or σ^2^ = $\frac{\sum_{}^{}(x - \mu)}{N}^{2}$ or Sample or
S^2^ = $\frac{\sum_{}^{}\left( x - \overline{x} \right)}{N - 1}^{2}$

Example:

This example shows how to calculate a sample variance.

Step 1. Compute the sample mean.

Step 2. Compute the deviation of each measurement from the mean:
(X-$\overline{X}$).

Step 3. Square each deviation: X-$\overline{X}$^2^.

Step 4. Sum the square deviations:
$\sum_{}^{}\left( X - \overline{X} \right)^{2}$.

Step 5. Divide the sum by (number of measurements -- 1).

### Sample Size/Frequency

Determining sample size is a very important issue because samples that
are too large may waste time, resources, and money, while samples that
are too small may lead to inaccurate results. In many cases, we can
easily determine the minimum sample size needed to estimate a process
parameter, such as the population mean µ.

When sample data is collected and the sample mean $\overline{x}$ is
calculated, that sample mean is typically different from the population
mean µ. This difference between the sample and population means can be
thought of as an error. The margin of error Ε is the maximum difference
between the observed sample mean $\overline{x}$ and the true value of
the population mean µ:

![](media/image36.png){width="0.9055555555555556in"
height="0.4583333333333333in"}

where:

![](media/image37.png){width="0.2604166666666667in"
height="0.3236111111111111in"} is known as the critical value, the
positive *z* value that is at the vertical boundary for the area of
![](media/image38.png){width="0.28194444444444444in"
height="0.3326388888888889in"} in the right tail of the standard normal
distribution

$\sigma$ is the population standard deviation

*n* is the sample size

Rearranging this formula, we can solve for the sample size necessary to
produce results accurate to a specified confidence and margin of error.

![](media/image39.png){width="0.8847222222222222in"
height="0.6659722222222222in"}

This formula can be used when you know $\sigma$ and want to determine
the sample size necessary to establish, with a confidence of 1-α, the
mean value µ to within ± Ε. You can still use this formula if you do not
know your population standard deviation $\sigma$ and you have a small
sample size. Although it is unlikely that you will know $\sigma$ when
the population mean is not known, you may be able to determine $\sigma$
from a similar process or from a pilot test/simulation.

### Error Analysis

No measurement is perfectly accurate or exact. Many instrumental,
physical, and human limitations cause measurements to deviate from the
true values of the quantities being measured. These deviations are
called experimental uncertainties, but more commonly the shorter word
"error" is used.

What is the true value of a measured quantity? We can think of it as the
value we would measure if we somehow eliminated all error from
instruments and procedure. We can improve the measurement process, of
course, but since we can never eliminate measurement errors entirely, we
can never hope to measure true values. We have only introduced the
concept of true value for purposes of discussion. When we specify the
error in a quantity or result, we are giving an estimate of how much
that measurement is likely to deviate from the true value of the
quantity. This estimate is far more than a guess for it is founded on a
physical analysis of the measurement process and a mathematical analysis
of the equations that apply to the instruments and to the physical
process being studied.

A measurement or experimental result is of little use if nothing is
known about the probable size of its error. We know nothing about the
reliability of a result unless we can estimate the probable sizes of the
errors and uncertainties in the data which were used to obtain that
result.

That is why it is important to learn how to determine quantitative
estimates of the nature and size of experimental errors, and to predict
how these errors affect the reliability of the final result. The
following discussion is designed to make the candidate aware of some
common types of errors and some simple ways to quantify them and analyze
how they affect results.

Experimental errors are of two types: (1) indeterminate and (2)
determinate (or systematic) errors.

Indeterminate errors. Indeterminate errors are present in all
experimental measurements. The name indeterminate indicates that there
is no way to determine the size or sign of the error in any individual
measurement. Indeterminate errors cause a measuring process to give
different values when that measurement is repeated many times.
Indeterminate errors can have many causes, including operator errors or
biases, fluctuating experimental conditions, varying environmental
conditions, and the inherent variability of measuring instruments.

The effect that indeterminate errors have on results can be somewhat
reduced by taking repeated measurements and then calculating their
average. The average is generally considered to be a better
representation of the true value than any single measurement because
errors of positive and negative sign tend to compensate each other in
the averaging process.

Determinate (or systematic) errors. The terms determinate error and
systematic error are synonyms. Systematic means that when the
measurement of a quantity is repeated several times, the error has the
same size and algebraic sign for every measurement. Determinate means
that the size and sign of the errors are determinable.

A common cause of determinate error is instrumental or procedural bias
(e.g., an incorrectly calibrated scale or instrument, a color-blind
observer matching colors). Another cause is outright experimental
blunder (e.g., using an incorrect value of a constant in the equations,
using the wrong units, reading a scale incorrectly). Every effort should
be made to minimize the possibility of such errors by careful
calibration of apparatuses and by the use of the best possible
measurement techniques.

Determinate errors can be more serious than indeterminate errors for
three reasons: (1) there is no sure method for discovering and
identifying them just by looking at the experimental data; (2) their
effects cannot be reduced by averaging repeated measurements; and (3) a
determinate error has the same size and sign for each measurement in a
set of repeated measurements, so there is no opportunity for positive
and negative errors to offset each other.

A measurement with relatively small indeterminate error is said to have
high precision. A measurement with small indeterminate error and small
determinate error is said to have high accuracy. Precision does not
necessarily imply accuracy. A precise measurement may be inaccurate if
it has a determinate error.

Deviation. When a set of measurements is made of a physical quantity, it
is useful to express the difference between each measurement and the
average (mean) of the entire set. This is called the deviation of the
measurement from the mean. Use the word deviation when an individual
measurement of a set is being compared with a quantity which is
representative of the entire set. Deviations can be expressed as
absolute amounts or as percents.

Difference. There are situations where we need to compare measurements
or results that are assumed to be about equally reliable, that is, to
express the absolute or percent difference between the two. For example,
you might want to compare two independent determinations of a quantity,
or to compare an experimental result with one obtained independently by
someone else or by another procedure. To state the difference between
two things implies no judgment about which is more reliable.

Experimental discrepancy. When a measurement or result is compared with
another that is assumed or known to be more reliable, we call the
difference between the two the experimental discrepancy. Discrepancies
may be expressed as absolute discrepancies or as percent discrepancies.
It is customary to calculate the percent by dividing the discrepancy by
the more reliable quantity (and to then, of course, multiply by 100).
However, if the discrepancy is only a few percent, it makes no practical
difference which of the two is in the denominator.

The experimental error \[uncertainty\] can be expressed in several
standard ways, as explained below.

Limits of error. Error limits may be expressed in the form Q ± q, where
Q is the measured quantity and q is the magnitude of its limit of error.
This expresses the experimenter's judgment that the true value of Q lies
between Q - q and Q + q. This entire interval within which the
measurement lies is called the range of error. Manufacturer performance
guarantees for laboratory instruments are often expressed this way.

Average deviation. This measure of error is calculated in this manner:
First calculate the mean (average) of a set of successive measurements
of a quantity, Q. Then find the magnitude of the deviations of each
measurement from the mean. Average these magnitudes of deviations to
obtain a number called the average deviation of the data set. It is a
measure of the dispersion (spread) of the measurements with respect to
the mean value of Q, that is, of how far a typical measurement is likely
to deviate from the mean. But this is not quite what is needed to
express the quality of the mean itself. We want an estimate of how far
the mean value of Q is likely to deviate from the true value of Q. The
appropriate statistical estimate of this is called the average deviation
of the mean.

Uncertainties may be expressed as absolute measures, giving the size of
a quantity's uncertainty in the same units as the quantity itself.

Example:

A piece of metal is weighed a number of times, and the average value
obtained is: M = 34.6 gm. By analysis of the scatter of the
measurements, the uncertainty is determined to be m = 0.07 gm. This
absolute uncertainty may be included with the measurement in this
manner:\
M = 34.6 ± 0.07 gm.

The value 0.07 after the ± sign in this example is the estimated
absolute error in the value 3.86.

## Chemical processing personnel shall demonstrate a working-level knowledge of pump theory and operation.

a)  Define the following terms as they relate to pumps:

-   Head

-   Net positive suction head

-   Cavitation

-   Shut-off head

-   Run-out

-   Centrifugal pump

-   Positive displacement pump

### Head

Head is the pressure generated by the height of a fluid.

### Net Positive Suction Head

Net positive suction head is the quantity used to determine if the
pressure of the liquid being pumped is adequate to avoid cavitation.

### Cavitation

Cavitation is the flow area at the eye of the pump impeller. It is
usually smaller than either the flow area of the pump suction piping or
the flow area through the impeller vanes. When the liquid that is being
pumped enters the eye of a centrifugal pump, the decrease in flow area
results in an increase in flow velocity, accompanied by a decrease in
pressure. The greater the pump flow rate, the greater the pressure drop
between the pump suction and the eye of the impeller. If the pressure
drop is large enough, or if the temperature is high enough, the pressure
drop may be sufficient to cause the liquid to flash to vapor when the
local pressure falls below the saturation pressure for the fluid being
pumped. Any vapor bubbles formed by the pressure drop at the eye of the
impeller are swept along the impeller vanes by the flow of the fluid.
When the bubbles enter a region where local pressure is greater than
saturation pressure, the vapor bubbles abruptly collapse. This process
of the formation and subsequent collapse of vapor bubbles in a pump is
called cavitation.

### Shut-Off Head

Shut-off head is the maximum head that can be developed by a centrifugal
pump operating at a set speed.

### Run-Out

Run-out is the maximum flow that can be developed by a centrifugal pump
without damaging the pump.

### Centrifugal Pump

Centrifugal pumps basically consist of a stationary pump casing and an
impeller mounted on a rotating shaft. The pump casing provides a
pressure boundary for the pump and contains channels to properly direct
the suction and discharge flow. The pump casing has suction and
discharge penetrations for the main flow path of the pump, and normally
has small drain and vent fittings to remove gases trapped in the pump
casing or to drain the pump casing for maintenance.

### Positive Displacement Pump

A positive displacement pump is one in which a definite volume of liquid
is delivered for each cycle of pump operation. This volume is constant
regardless of the resistance to flow offered by the system the pump is
in, provided the capacity of the power unit driving the pump or pump
component strength limits are not exceeded. The positive displacement
pump delivers liquid in separate volumes with no delivery in between,
although a pump having several chambers may have an overlapping delivery
among individual chambers, which minimizes this effect. The positive
displacement pump differs from centrifugal pumps, which deliver a
continuous flow for any given pump speed and discharge resistance.

l)  Describe the general principle of operation for centrifugal pumps.

The pump casing guides the liquid from the suction connection to the
center, or eye, of the impeller. The vanes of the rotating impeller
impart a radial and rotary motion to the liquid, forcing it to the outer
periphery where it is collected in the outer part of the pump casing
called the volute. The volute is a region that expands in a
cross-sectional area as it wraps around the pump casing. The purpose of
the volute is to collect the liquid discharged from the periphery of the
impeller at high velocity and gradually cause a reduction in fluid
velocity by increasing the flow area. This converts the velocity head to
static pressure. The fluid is then discharged from the pump through the
discharge connection.

m)  Describe the general principle of operation for positive
    displacement pumps.

All positive displacement pumps operate on the same basic principle.
This principle can be most easily demonstrated by considering a
reciprocating positive displacement pump consisting of a single
reciprocating piston in a cylinder with a single suction port and a
single discharge port. Check valves in the suction and discharge ports
allow flow in only one direction. During the suction stroke, the piston
moves to the left, causing the check valve in the suction line between
the reservoir and the pump cylinder to open and admit water from the
reservoir. During the discharge stroke, the piston moves to the right,
seating the check valve in the suction line and opening the check valve
in the discharge line. The volume of liquid moved by the pump in one
cycle (one suction stroke and one discharge stroke) is equal to the
change in the liquid volume of the cylinder as the piston moves from its
farthest left position to its farthest right position.

n)  Using a cutaway drawing of a centrifugal pump, identify the
    following components and discuss their purpose:

-   Impeller

-   Packing or mechanical seal

-   Volute

-   Lantern ring

-   Wearing rings (impeller and/or casing)

This is a performance-based competency. The qualifying official will
evaluate the completion of this competency.

o)  Discuss why centrifugal pumps should normally be started against a
    shut-off head, and the hazards associated with continuously running
    against a shut-off head.

By starting a pump at a shut-off head, cavitation is minimized by
maximizing net positive suction head. If you maintain the shut-off head
as the pump runs, the temperature will increase, and eventually you will
begin to get cavitation in the pump.

p)  State the dangers to personnel and equipment associated with
    starting a positive displacement pump against a shut-off head.
    Discuss the importance and methods of providing over pressurization
    protection for positive displacement pumps.

Operating a positive displacement pump at shut-off head can lead to
lifting of the relief valve. All systems with positive displacement
pumps are required to have relief valves. Without these valves, pipe
systems could fail, and in the long term, cause severe damage to a
facility or injure or kill personnel. Each positive displacement pump
should have its own individual relief valve.

q)  Compare and contrast the principle of operation and typical pumped
    medium of the following types of positive displacement pumps:

-   Reciprocating

-   Rotary-screw

-   Vane-axial

Reciprocating pumps are thought of as simple plunger-type pumps.
Rotary-screw pumps remind you of several screws being screwed down while
in use. A vane-axial pump looks somewhat like a distorted centrifugal
pump. The reciprocating pump is a simple back and forth plunger that
increases pressure. The rotary-screw pump uses a simple screwing motion
to increase the pressure of the fluid. The vane-axial pump uses a
centered cylinder and moving vanes to impart energy on the fluid. All
add a positive pressure to a fluid, but each pump has a use which is
preferred. Vane-axial pumps may be used for liquids or gases, while
rotary-screw pumps and reciprocating pumps are mostly used for liquids.

r)  Using the following list of system and/or pumped medium
    characteristics, identify which type of pump (e.g., centrifugal,
    reciprocating positive displacement, rotary-screw positive
    displacement) is best suited for the application.

-   Slurries

-   Fluids with high viscosities

-   Low volume, high head

-   Low head, high volume

-   Water

-   Oil

This is a performance-based competency. The qualifying official will
evaluate the completion of this competency.

s)  Discuss the concept of pump cavitation and describe its harmful
    effects.

The flow area at the eye of the pump impeller is usually smaller than
either the flow area of the pump suction piping or the flow area through
the impeller vanes. When the liquid that is being pumped enters the eye
of a centrifugal pump, the decrease in flow area results in an increase
in flow velocity, accompanied by a decrease in pressure. The greater the
pump flow rate, the greater the pressure drop between the pump suction
and the eye of the impeller. If the pressure drop is large enough, or if
the temperature is high enough, the pressure drop may be sufficient to
cause the liquid to flash to vapor when the local pressure falls below
the saturation pressure for the fluid being pumped. Any vapor bubbles
formed by the pressure drop at the eye of the impeller are swept along
the impeller vanes by the flow of the fluid. When the bubbles enter a
region where local pressure is greater than saturation pressure farther
out the impeller vane, the vapor bubbles abruptly collapse. This process
of the formation and subsequent collapse of vapor bubbles in a pump is
called cavitation. Cavitation in a centrifugal pump has a significant
effect on pump performance. Cavitation degrades the performance of a
pump, resulting in a fluctuating flow rate and discharge pressure.
Cavitation can also be destructive to a pump's internal components. When
a pump cavitates, vapor bubbles form in the low-pressure region directly
behind the rotating impeller vanes. These vapor bubbles then move toward
the oncoming impeller vane, where they collapse and cause a physical
shock to the leading edge of the impeller vane. This physical shock
creates small pits on the leading edge of the impeller vane. Each
individual pit is microscopic in size, but the cumulative effect of
millions of these pits formed over a period of hours or days can
literally destroy a pump impeller. Cavitation can also cause excessive
pump vibration, which could damage pump bearings, wearing rings, and
seals.

## Chemical processing personnel shall demonstrate a working-level knowledge of fluid mechanics and properties.

a)  Define the following:

-   Temperature

-   Pressure

-   Viscosity

-   Specific volume

-   Specific gravity

-   Capillarity

-   Laminar flow

-   Turbulent flow

-   Uniform flow

-   Surface tension

### Temperature

Temperature is a measure of the energy in a substance. The more heat
energy in the substance, the higher the temperature will be.

### Pressure

Pressure is the measure of the force that acts on a unit area.

### Viscosity

Viscosity is a measure of resistance to flow in a liquid.

### Specific Volume

Specific volume is the volume per unit mass; the reciprocal of density.

### Specific Gravity

Specific gravity is the ratio of the density of any substance to the
density of some other substance taken as standard, with water being the
standard for solids.

### Capillarity

Capillarity is the action by which the surface of a liquid where it is
in contact with a solid, as in a capillary tube, is elevated or
depressed depending on the relative attraction of the molecules of the
liquid for each other and for those of the solid.

### Laminar Flow

Laminar flow is smooth and regular fluid flow, with the direction of
motion at any point remaining constant as if the fluid were moving in a
series of layers sliding over one another without mixing.

### Turbulent Flow

Turbulent flow is flow in which the flow lines are confused and the
fluid is heterogeneously mixed.

### Uniform Flow

Uniform flow occurs when a flow's depth and width are constant.

### Surface Tension

Surface tension is a property of liquid surfaces that causes the surface
layer to behave like a thin, elastic "skin." Molecules in a liquid have
attractive forces that hold them together. Molecules on the surface are
attracted to molecules from all sides and below, but not from above.
This results in a downward and sideways pull on molecules on the surface
layer.

t)  Explain the equation of continuity as it applies to fluid flow.

The equation of continuity involves a partial differential equation
involving the derivatives of density and velocity. The equation is
applied to a system in which velocity and density are continuum
functions.

u)  Discuss the Reynold's number and how it is used.

A dimensionless combination of variables important in the study of
viscous flow is called the Reynold's number.

The Reynold's number is important in analyzing any type of flow when
there is substantial velocity gradient shear. The Reynold's number
indicates the relative significance of the viscous effect compared to
the inertia effect. The Reynold's number is proportional to inertial
force divided by viscous force.

The Reynold's number can be expressed as:

![](media/image40.png){width="4.406944444444444in"
height="2.397222222222222in"}

v)  Discuss Bernoulli's equation as it applies to steady-state flow rate
    calculations.

Bernoulli's equation results from the application of the general energy
equation and the first law of thermodynamics to a steady flow system in
which no work is done on or by the fluid, no heat is transferred to or
from the fluid, and no change occurs in the internal energy (i.e., there
is no temperature change) of the fluid. Under these conditions, the
general energy equation is simplified to the following:

(PE + KE + PV)1 = (PE + KE + PV)2

## Chemical processing personnel shall demonstrate the ability to calculate flow rates in fluid systems.

a)  For non-compressible fluids, calculate flow rates using the
    following methods:

-   Volume flow rate

-   Mass flow rate

-   Steady-state continuity equation

-   Bernoulli's equation

-   Darcy's formula

This is a performance-based competency. The qualifying official will
evaluate the completion of this competency.

w)  Discuss the limitations of the above methods.

### Volume Flow Rate

Volume flow rate is not a vector definition, which means that there is
no identifiable difference in inflow and outflow by definition.

### Mass Flow Rate

Mass flow rate is directly affected by the density of the fluid. As
density changes, the mass flow rate changes accordingly.

### Stead-State Continuity Equation

The steady-state continuity equation implements density and velocity,
which are continuum functions, and the equation does not allow for any
source or sink singularities within the element.

### Bernoulli's Equation

Bernoulli's equation assumes the following limitations: all fluids are
viscous and they all have friction losses.

### Darcy's Formula

Darcy's formula calculates friction losses in a pipe, but requires that
you know the type of flow and the type of pipe that is being solved for.

## Chemical processing personnel shall demonstrate a working-level knowledge of thermodynamics.

a)  Define the following:

-   Compression

-   Isothermic

-   Isentropic

-   Adiabatic

-   Heat of Dilution

-   Specific Heat

### Compression

Compression is the process by which the working substance in a heat
engine, such as the vapor mixture in the cylinder of an
internal-combustion engine, is compressed.

### Isothermic

Isothermic describes a process that maintains the temperature constant
throughout the system.

### Isentropic

Isentropic describes an adiabatic process in which there is no change in
system entropy.

### Adiabatic

Adiabatic describes a process in which no heat or other energy crosses
the system boundary.

### Heat of Dilution

The heat of dilution (from molality m) to infinite dilution is the
enthalpy change per mol salt when a solution of molality m is diluted to
infinite dilution. The heat of dilution to infinite dilution is the
excess enthalpy relative to the infinitely diluted solution.

### Specific Heat

The specific heat is the amount of heat per unit mass required to raise
the temperature by one degree Celsius.

x)  Discuss entropy and enthalpy as they relate to chemical processes
    and performing energy balances.

### Entropy

For a closed thermodynamic system, entropy is a quantitative measure of
the amount of thermal energy not available to do work.

### Enthalpy

Enthalpy is a thermodynamic function of a system equivalent to the sum
of the internal energy of the system plus the product of its volume
multiplied by the pressure exerted on it by its surroundings.

y)  Define and discuss the following:

-   Carnot cycle

-   Rankine cycle

### Carnot Cycle

The Carnot cycle is composed of four reversible processes. Two of the
processes are isothermal and two are adiabatic. The Carnot cycle can be
executed in either a closed or steady flow system.

### Rankine Cycle

The Rankine cycle is the model for the steam power plant and, in its
most basic form, consists of four components.

z)  Read and interpret a Mollier diagram.

a)  Using data from a steady-state system, calculate the following:

-   Entropy change

-   Enthalpy change

-   Pressure

-   Temperature

Elements "d" and "e" are performance-based competencies. The qualifying
official will evaluate the completion of these competencies.

## Chemical processing personnel shall demonstrate a working-level knowledge of steady-state heat transfer.

a)  Define:

-   Conduction

-   Convection

-   Radiation

-   Thermal conductivity

### Conduction

Conduction is the transfer of heat by the interactions of atoms or
molecules of a material through which the heat is being transferred.

### Convection

Convection is the transfer of heat by the mixing and motion of
macroscopic portions of a fluid.

### Radiation

Radiation is the transfer of heat by electromagnetic radiation that
arises due to the temperature of a body.

### Thermal Conductivity

Thermal conductivity is a measure of a substance's ability to transfer
heat through itself.

b)  Discuss Fourier's law.

Fourier's law is an empirical law based on observation. It states that
the rate of heat flow, d**Q**/d**t**, through a homogenous solid is
directly proportional to the area, **A**, of the section at right angles
to the direction of heat flow, and to the temperature difference along
the path of heat flow.

c)  Describe the factors that contribute to the co-efficient of thermal
    conductivity.

When heat is applied to a portion of a material, that heat will move
through the material. This movement of heat through a material is called
the thermal current. Depending on the composition of the atoms of that
material, the heat may move very slowly, or it may move very quickly.
This dependence is quantified by the coefficient of thermal
conductivity. Each material has a unique coefficient of thermal
conductivity. A high coefficient means heat moves very quickly; a low
coefficient means heat moves very slowly.

d)  Calculate the heat flux for one-dimensional, steady-state heat
    transfer through the following:

-   Composite wall

-   Series wall

-   Parallel wall

e)  Using data, calculate total heat transfer and local heat flux in a
    laminar flow system.

Elements "d" and "e" are performance-based competencies. The qualifying
official will evaluate the completion of these competencies.

## Chemical processing personnel shall demonstrate a working-level knowledge of the construction and operation of heat exchangers.

a)  Describe the principle of operation for the following types of heat
    exchangers:

-   Shell and tube

-   Fin and tube

-   Cooling tower

### Shell and Tube

In a shell and tube heat exchanger, the shell side usually contains the
process fluid, and the tube side contains water from the town mains or a
cooling tower, or an ethylene glycol solution from a chiller unit. Flow
may be in parallel or cross flow for the heat exchanger.

### Fin and Tube

In a fin and tube heat exchanger, the fin is used to increase the
surface area to allow for greater heat transfer from the process fluid.
The tube side contains the water or other cooling medium for the heat
exchanger.

### Cooling Tower

The typical function of a cooling tower is to cool the water of a steam
power plant by air that is brought into direct contact with the water.
The water is mixed with vapor that diffuses from the condensate into the
air. The formation of the vapor requires a considerable removal of
internal energy from the water; the internal energy becomes latent heat
of the vapor. Heat and mass exchange are coupled in this process, which
is a steady-state process like the heat exchange in the ordinary heat
exchanger.

f)  Define the following terms as they apply to heat exchangers:

-   Tube sheet

-   Tell-tale drain

-   Parallel flow

-   Counter flow

-   Cross flow

### Tube Sheet

A tube sheet is the separation between the water box areas and the steam
condensing areas of a condenser. The cooling water tubes are attached to
the tube sheet. The cooling water tubes are supported within the
condenser by the tube support sheets.

### Tell-Tale Drain

A tell-tale drain is a drain placed between the two parts of the tube
sheet to indicate a leak in either the water box side or the process
fluid side.

### Parallel Flow

Parallel flow exists when both the tube side fluid and the shell side
fluid flow in the same direction. In this case, the two fluids enter the
heat exchanger from the same end with a large temperature difference. As
the fluids transfer heat, hotter to cooler, the temperatures of the two
fluids approach each other.

### Counter Flow

Counter flow exists when the two fluids flow in opposite directions. The
two fluids enter the heat exchanger at opposite ends. Because the cooler
fluid exits the counter flow heat exchanger at the end where the hot
fluid enters the heat exchanger, the cooler fluid will approach the
inlet temperature of the hot fluid. Counter flow heat exchangers are the
most efficient of the three types. In contrast to the parallel flow heat
exchanger, the counter flow heat exchanger allows the hottest cold-fluid
temperature to be greater than the coldest hot-fluid temperature.

### Cross Flow

Cross flow exists when one fluid flows perpendicular to the second
fluid; that is, one fluid flows through tubes, and the second fluid
passes around the tubes at a 90° angle. Cross flow heat exchangers are
usually found in applications where one fluid changes state (two-phase
flow). An example is a steam system's condenser in which the steam
exiting the turbine enters the condenser shell side, and the cool water
flowing in the tubes absorbs the heat from the steam, condensing it into
water. Large volumes of vapor may be condensed using this type of heat
exchanger flow.

g)  Using a cutaway drawing of the following types of heat exchangers,
    show the flow paths of the cooling medium and the medium to be
    cooled:

-   Parallel flow

-   Counter flow

-   Cross flow

This is a performance-based competency. The qualifying official will
evaluate the completion of this competency.

h)  Using data, calculate the log mean temperature difference for heat
    exchangers.

This is a performance-based competency. The qualifying official will
evaluate the completion of this competency.

i)  Explain the principle of operation of a forced-draft cooling tower.

Forced-draft cooling towers are very similar to induced-draft cooling
towers. The primary difference is that the air is blown in at the bottom
of the tower and exits at the top. Forced-draft cooling towers are the
forerunner to induced-draft cooling towers. Water distribution problems
and recirculation difficulties discourage the use of forced-draft
cooling towers.

j)  Explain the principle of operation of a natural-draft (parabolic)
    cooling tower.

Natural-convection cooling towers use the principle of convective flow
to provide air circulation. As the air inside the tower is heated, it
rises through the tower. This process draws more air in, creating a
natural air flow to provide cooling of the water. The basin at the
bottom of the tower is open to the atmosphere. The cooler, denser air
outside the tower will flow in at the bottom and contribute to the air
circulation within the tower. The air circulation will be
self-perpetuating due to the density difference between the warmer air
inside and the cooler air outside.

## Chemical processing personnel shall demonstrate a working-level knowledge of the components, operation, and theory of pneumatic systems.

a)  Define the following terms and discuss their relationship:

-   Dew point

-   Dehydrator

-   Dew point indicator

-   Actuator

### Dew Point

The dew point is the point at which the moisture in the air begins to
condense in a constant pressure condition. In a pneumatic system, the
dew point is important to prevent water from forming in the air system.

### Dehydrator

The dehydrator removes moisture contained in the air or some other
pneumatic gas. This helps to minimize the amount of moisture that may
form and to reduce the dew point temperature.

### Dew Point Indicator

A dew point indicator is an instrument for measuring the relative
humidity or moisture content of a gas by measuring its dew point.

### Actuator

An actuator is a hydraulic, electric, or pneumatic device used to move
an object. In a hydraulic system, an actuator may impart energy on the
system or allow for operation of the system.

k)  Describe the basic operation of a pneumatic system.

In a pneumatic system, the compressor feeds air into a main tank. The
main tank's pressure is higher than the pressure required by any single
pneumatic component. The main tank outlet should have an adjustable
regulator, which reduces the tank's pressure to that required by the
rest of the pneumatic system. On the regulator are two gauges used to
read both tank pressure and the output pressure of the regulator. The
compressor's output line should be coupled with a filter/drier trap
unit, which is designed to remove oil and any foreign particles that may
have been introduced by the compressor. It is also intended to collect
any water which condenses out of the air as it passes through. Water and
debris (including tiny metal particles shed by the compressor's
mechanism) contribute to rust, corrosion, and wear, while oil causes
deterioration in rubber parts and seals. Thus, a filter can be important
for reliable system operation. At the bottom of the glass is a tap valve
which may be opened during operation to expel water and oil. The unit
should be checked regularly, and the excess water must be bled off
before it reaches the level of the filter. In humid climates, this can
occur frequently if the trap is small. As air hoses run to multiple
applications, they branch by means of splitters and valves from the main
line. The master air storage tank at the compressor holds a surplus of
air as a buffer.

l)  Discuss how energy in a pneumatic system is converted to work.

The stored energy in the air system is applied to actuators, pistons, or
other mechanical components to operate these components. The air
operates these components to allow system operation.

m)  Discuss the hazardous relationship between high-pressure air and
    oil.

If oil is pressurized by compressed air, an explosive hazard exists if
the high-pressure air comes into contact with the oil because it may
create a diesel effect and subsequent explosion. A carefully followed
preventive maintenance plan is the best precaution against explosion.

n)  Identify and discuss the general hazards associated with pneumatic
    systems and their components and the over-pressurization of these
    systems.

People often lack respect for the power in compressed air because air is
so common and is often viewed as harmless. At sufficient pressures,
compressed air can cause serious damage if handled incorrectly. To
minimize the hazards of working with compressed air, all safety
precautions should be followed closely. Small leaks or breaks in the
compressed air system can cause minute particles to be blown at
extremely high speeds. Always wear safety glasses when working in the
vicinity of any compressed air system. Safety goggles are recommended if
contact lenses are worn. Compressors can make an exceptional amount of
noise while running. The noise of the compressor, in addition to the
drain valves lifting, creates enough noise to require hearing
protection. The area around compressors should normally be posted as a
hearing protection zone. Pressurized air can do the same type of damage
as pressurized water. Treat all operations on compressed air systems
with the same care taken on liquid systems. Closed valves should be
slowly cracked open, and both sides should be allowed to equalize prior
to opening the valve further. Systems being opened for maintenance
should always be depressurized before work begins. Over-pressurization
of the system could lead to system and component failure that could lead
to injury.

o)  Discuss the hazards associated with portable gases such as cylinders
    of oxygen, nitrogen, etc.

Refer to 29 CFR 1910, sections 101--105.

## Chemical processing personnel shall demonstrate a working-level knowledge of the basic components, operations, and theory of hydraulic systems.

a)  Define the following terms and discuss their relationship in
    hydraulic systems:

-   Force

-   Work

-   Pressure

-   Reservoir

-   Accumulator

-   Actuator

### Force

Force is the push or pull that one body exerts on another, including
gravitational, electrostatic, magnetic, and contact influence. In
hydraulic systems, fluid is used to transmit force through the system.

### Work

Work is the act of changing the energy of a particle, body, or system.
In a hydraulic system, work is performed by the fluid operating
components such as pistons and rams.

### Pressure

Pressure is the force applied to a unit area of surface. The system
pressure is what allows the hydraulics to transmit energy over a given
time.

### Reservoir

A reservoir is a tank used for collecting and storing a liquid.
Hydraulic systems use reservoirs to supply makeup volumes to the
systems.

### Accumulator

An accumulator is a container in which fluid is stored under pressure as
a source of fluid power. It is the hydraulic system makeup volume used
during operations that is kept under pressure to allow for hydraulic
surges.

### Actuator

An actuator is a hydraulic, electric, or pneumatic device used to move
an object. In a hydraulic system, an actuator may impart energy on the
system or allow for operation of the system.

p)  Describe the basic operation of a hydraulic system.

In a hydraulic system, oil from a tank or reservoir flows through a pipe
into a pump. Often a filter is provided on the pump suction to remove
impurities from the oil. The pump, usually a gear-type, positive
displacement pump, can be driven by an electric motor, an air motor, a
gas or steam turbine, or an internal combustion engine. The pump
increases the pressure of the oil. The actual pressure developed depends
upon the design of the system. Most hydraulic systems have some method
of preventing overpressure. One method of pressure control involves
returning hydraulic oil to the oil reservoir. The pressure control box
is usually a relief valve that provides a means of returning oil to the
reservoir upon overpressurization. The high-pressure oil flows through a
control valve (directional control). The control valve changes the
direction of oil flow, depending upon the desired direction of the load.
The load can be moved to the left or to the right by changing the side
of the piston to which the oil pressure is applied. The oil that enters
the cylinder applies pressure over the area of the piston, developing a
force on the piston rod. The force on the piston rod enables the
movement of a load or device. The oil from the other side of the piston
returns to a reservoir or tank.

q)  Discuss how energy in a hydraulic system is converted to work.

Oil from a tank or reservoir flows through a pipe into a pump. The pump
can be driven by a motor, a turbine, or an engine. The pump increases
the pressure of the oil. The high-pressure oil flows in the piping
through a control valve. The control valve changes the direction of the
oil flow. A relief valve, set at a desired safe-operating pressure,
protects the system from an overpressure condition. Oil entering the
cylinder applies pressure to the piston, developing a force on the
piston rod.

r)  Discuss the purpose and basic construction of a hydraulic reservoir.

The reservoir is typically a tank used to store makeup hydraulic fluid.
The tank is usually connected to the suction of a pump and vented to
atmosphere. The reservoir has an indicator of level or volume that is
present in the tank.

s)  Discuss the purpose and basic construction of a hydraulic
    accumulator.

The accumulator acts as a surge volume/makeup volume for the system
during operations. This accumulator is normally under pressure using air
to maintain the accumulator pressure equal to system pressure.

t)  Identify and discuss the hazards associated with hydraulic systems
    and their components.

Any use of a pressurized medium can be dangerous. Hydraulic systems
carry all the hazards of pressurized systems and special hazards that
are related directly to the composition of the fluid used. When using
oil as a fluid in a high-pressure hydraulic system, the possibility of
fire or an explosion exists. A severe fire hazard is generated when a
break in the high-pressure piping occurs and the oil is vaporized into
the atmosphere. Extra precautions against fire should be practiced in
these areas. If oil is pressurized by compressed air, an explosive
hazard exists if the high-pressure air comes into contact with the oil
because it may create a diesel effect and subsequent explosion. A
carefully followed preventive maintenance plan is the best precaution
against explosion.

## Chemical processing personnel shall demonstrate a working-level knowledge of Project and Contract Management.

a)  Discuss the phases of a project lifecycle as described in DOE O
    413.3. Briefly describe each of the critical decision points.

The acquisition management system establishes a management process to
translate user needs and technological opportunities into reliable and
sustainable facilities, systems, and assets that provide the required
mission capability. The system is organized by phases and critical
decisions. The Deputy Secretary serves as the Secretarial Acquisition
Executive (SAE) for the Department. As the SAE, he/she promulgates
Department-wide policy and direction, and personally makes critical
decisions for major system projects. Designated acquisition executives
(AE) make critical decisions for non-major system projects. The phases
represent a logical maturing of broadly stated mission needs into
well-defined technical, system, safety, and quality requirements, and
ultimately into operationally effective, suitable, and affordable
facilities, systems, and other end products.

### Phases of a Project Lifecycle

There are four phases of a project lifecycle. They are initiation,
definition, execution, and transition/closeout. The brief description of
each phase follows.

Initiation phase. During the initiation phase, identified user needs are
analyzed for consistency with the Department's strategic plan,
congressional direction, administration initiatives, and political and
legal issues. One outcome of the analysis could be a determination that
a user need exists that cannot be met through other than material means.
This outcome leads to the development and approval of a mission need
statement that discusses the user need in terms of required capability,
and not equipment, facilities, or other specific products. This is the
initial critical decision of the acquisition process (Critical Decision
0 --- Approve Mission Need). The information developed during this phase
also provides the basis for the project engineering and design budget
request when preliminary design activities are planned.

Definition phase. Upon approval of mission need, the project enters the
definition phase where alternative concepts based on user requirements,
risks, costs, and other constraints are analyzed to arrive at a
recommended alternative. This is accomplished using systems engineering
and other techniques and tools, such as alternatives analysis and value
management, to ensure the recommended alternative provides the essential
functions and capability at the optimum life-cycle cost, consistent with
required performance, scope, schedule, and cost. During this phase, more
detailed planning is accomplished which further defines the required
capability. These efforts include conceptual design, requirements
definition, risk analysis and management planning, and development of
the acquisition strategy. The products produced by this planning provide
the detail necessary to develop a rough order of magnitude or range for
the project cost and schedule. The recommended alternative, when
sufficiently defined and analyzed, is presented to the SAE or designated
AE for review and approval (Critical Decision 1 --- Approve Alternative
Selection and Cost Range).

Execution phase. Upon completing the definition phase, the project
enters the execution phase where the focus is on further defining the
selected alternative, developing preliminary designs, arriving at a high
confidence baseline, and generating the complete project execution plan,
all of which support a request for funds in the DOE budget. This part of
the execution phase culminates with the development of the performance
baseline, which is presented to the SAE or designated AE for approval
(Critical Decision 2 --- Approve Performance Baseline). The performance
baseline documents the Department's commitment to Congress to execute
the project at a specific cost and schedule threshold and achieve a
specific performance capability. After Critical Decision 2, engineering
and design continue until the project is ready for construction or
implementation.

Before major budget and other resources for construction or
implementation are committed, an executability review is performed as a
precursor to the next critical decision (Critical Decision 3 --- Approve
Start of Construction).

Transition/closeout phase. The transition/closeout phase is when the
project is approaching completion and has progressed into formal
transition, which generally includes final testing, inspection, and
documentation, as the project is prepared for operation, long-term care,
or closeout. Once implementation is substantially complete, transition
to operations begins. The transition point will depend on the type of
project. A project may seek approval to transition to operations
(Critical Decision 4 --- Approve Start of Operations or Project
Closeout) when required capability is implemented and functioning, and
operational resources are in place, have been trained, and are able to
perform their continuing responsibilities.

### Critical Decisions

Critical decisions identify the exit from one phase of the project and
the entry to the succeeding phase. As previously stated, each decision
marks an increase in commitment of resources, and is based on a
successful and complete preceding phase. At the most fundamental level,
the decisions confirm the following:

-   There is a need which cannot be met through nonmaterial means.

-   The selected alternative and approach is the right solution.

-   A definitive cost, scope, and schedule baseline has been developed.

-   The project is ready for implementation.

-   The project is ready for turnover or transition to operations.

There is no defined or directed period of time between decisions. Many
projects are able to quickly proceed through the early decision points
because of the lack of complexity or the presence of constraints that
reduce available alternatives, or the absence of significant technology
and developmental requirements. In these cases, decisions may be made
simultaneously.

All projects with a total project cost greater than \$5 million shall
use the defined critical decisions:

-   Critical Decision 0 --- Approve Mission Need

-   Critical Decision 1 --- Approve Alternative Selection and Cost Range

-   Critical Decision 2 --- Approve Performance Baseline

-   Critical Decision 3 --- Approve Start of Construction

-   Critical Decision 4 --- Approve Start of Operations or Project
    Closeout

Critical Decision 0 --- Approve Mission Need. A mission need statement
documents a mission requirement that the Department cannot meet through
nonmaterial means. It is the primary document supporting Critical
Decision 0 --- Approve Mission Need. Mission needs are identified in
terms of capability, and not in terms of equipment, facility, or other
solutions. Mission needs must support DOE's strategic plan and lower
level plans for each program. Approval of the mission need is the
authorization to develop alternative concepts and functional
requirements. A mission need statement should be developed for projects
having a total project cost greater than \$5 million, and should be
reviewed by the Office of Management, Budget, and Evaluation (OMBE)
prior to approval. For other than NNSA projects, the Program Secretarial
Officer (PSO) may request a waiver to the OMBE review for projects under
\$100 million. The waiver request shall be submitted to the Director,
Office of Program Analysis and Evaluation, at least 60 days in advance
of Critical Decision 0. The request must stipulate that the PSO has
reviewed all mission need requirements and must include a brief
statement as to why the OMBE review should be waived. The Director,
Office of Program Analysis and Evaluation, will notify the requesting
official in writing of the decision on the waiver request. For NNSA
projects under \$100 million, the above waiver process applies, except
that the NNSA Administrator may grant waivers to the OMBE review after
seeking the advice of OMBE. If the Administrator rejects the advice of
OMBE, he/she should seek the approval of the Deputy Secretary prior to
granting the waiver.

Mission need statements are approved by the PSOs/Deputy Administrators.
Delegation below this level is not allowed. Approval of the mission need
statement document does not represent approval of Critical Decision 0
for major system projects and other projects where the AE authority lies
above the PSO/Deputy Administrator level. In those cases, the key
elements of the mission need statement should be presented to the SAE/AE
as part of the decision-making process.

Critical Decision 0 --- Approve Mission Need. Critical Decision 0
formally establishes a project and initiates a requirement for project
status reporting. The DOE Project Assessment and Reporting System (PARS)
provides a web-based system to report project status. Starting at
Critical Decision 0, project status should be reported monthly using the
PARS, and the AE should begin conducting quarterly progress reviews. The
Office of Engineering and Construction Management (OECM) shall be
invited to all quarterly reviews. The requirement for quarterly reviews
cannot be delegated below the AE for non-major system projects. The SAE
may delegate quarterly reviews for major system projects to the Under
Secretary/National Nuclear Security Administration (NNSA) Administrator.

Critical Decision 1 --- Approve Alternative Selection and Cost Range.
Key activities that take place leading up to Critical Decision 1 include
alternative and requirements analysis, conceptual design, development of
an acquisition strategy, evaluation of project risks, hazards analysis,
systems engineering, and value management.

Requirements related to Critical Decision 1 are as follows:

-   Requirements that form the basis for the design and engineering
    phase of the project shall be clearly documented.

-   A conceptual design report should be developed that

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-   includes a clear and concise description of the alternatives
    analyzed, the basis for the alternative selected, how the
    alternative meets the approved mission need, and the
    functions/requirements that define the alternative;

-   demonstrates the capability for success.

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-   An acquisition strategy that accounts for risks and mitigation
    strategies should be developed for each project, and shall be
    reviewed by OMBE prior to approval by the designated PSO or NNSA
    Deputy/Associate Administrator. For other than NNSA projects, the
    PSO may request a waiver to the OMBE review for projects under \$100
    million. The waiver request shall be submitted to the Director,
    Office of Engineering and Construction Management, at least 60 days
    in advance of Critical Decision 1. The request must stipulate that
    the PSO has reviewed all acquisition strategy requirements, and must
    include a brief statement as to why the OMBE review should be the
    requesting official in writing of the decision on the waiver
    request. For NNSA projects under \$100 million, the above waiver
    process applies, except that the NNSA Administrator may grant
    waivers to the OMBE review after seeking the advice of OMBE. If the
    Administrator rejects the advice of OMBE, he shall seek the approval
    of the Deputy Secretary prior to granting the waiver.

-   All projects should include a value management assessment. The
    assessment should be conducted as part of the conceptual design
    process to include making a determination of whether a formal value
    engineering study is required. Any decision to not perform a formal
    value engineering study shall be documented in the project execution
    plan.

At the conclusion of the concept exploration process, the alternative
selected as the best solution to a mission need is presented for
approval. While a range of costs, schedule, and performance bound the
solution/alternative, there is no committed or approved baseline until
the design matures --- when estimates and schedules can be defined with
an acceptable degree of certainty. The approval package must include a
description of alternatives considered, trade studies, development
efforts, and testing requirements. Approval of the alternative selection
and cost range authorizes the beginning of preliminary design work.

Critical Decision 2 --- Approve Performance Baseline. The performance
baseline defines the cost, schedule, performance, and scope commitment
to which the Department will execute the project. The performance
baseline is generally the result of a mature design; detailed,
resource-loaded schedules and cost estimates for the entire project; and
the defined performance parameters and scope. Approval of the
performance baseline marks the beginning of performance tracking. It
also authorizes submission of the total project budget request. Key
activities that take place leading up to the approval include
preliminary design; development of key performance, scope and schedule
parameters; risk assessment; establishment of a performance measurement
system; identification of project interfaces; and development of the
project execution plan. Design may proceed throughout this phase of the
project. However, if the project scope or cost has changed significantly
from that which was identified in the conceptual design, the AE should
weigh the risk of continuing the design against the potential need to
revise the project scope or re-examine the alternatives available to
satisfy the mission need.

Requirements related to Critical Decision 2 include the following:

-   A project execution plan should be developed for each project and
    should include an accurate reflection of how the project is to be
    accomplished, resource requirements, technical considerations, risk
    management, and roles and responsibilities.

-   All projects should establish a performance baseline at Critical
    Decision 2 that includes key performance parameters to clearly
    establish the capabilities being acquired and the schedule and total
    cost to acquire the capability.

-   The performance baseline should account for risks and mitigation
    strategies, and should be adjusted for both durations and costs,
    providing a realistic, achievable performance baseline commitment.

-   OMBE will validate all performance baselines prior to approval. An
    external independent review should be performed by OMBE to support
    the baseline validation.

-   Every project should have a functioning performance management
    system no later than final performance baseline approval.

-   For projects with a total projected cost greater than \$20 million,
    the performance management system should be an earned value
    management system that is certified as compliant with ANSI/EIA-748.
    For projects executed under time-and-material contracts, firm
    fixed-price contracts, or level of effort support contracts, the AE
    may approve an alternative performance management system. The
    alternative performance management system must be described in the
    project execution plan.

-   Starting at Critical Decision 2, project performance shall be
    reported monthly using PARS.

Critical Decision 3 --- Approve Start of Construction. Approve Start of
Construction provides authorization to complete all procurement and
construction and/or implementation activities, and the planning,
implementing, and completion of all acceptance and turnover activities.
This authorizes the project to commit all the resources necessary,
within the funds provided, to execute the project. An executability
external independent review will be conducted by OMBE prior to Critical
Decision 3 for all major system projects.

Critical Decision 4 --- Approve Start of Operations or Project Closeout.
Approve Start of Operations or Project Closeout is approval to
transition or turnover to operations. It is predicated on the readiness
of the operators to operate and maintain the system, facility, or
capability. Transition and turnover does not necessarily terminate all
project activity. It marks a point at which the operations organization
assumes responsibility for the operation and maintenance. All projects
should have a project transition/closeout plan that clearly defines the
basis for attaining initial operating capability, full operating
capability, or project closeout, as applicable. The closeout/transition
plan is normally included in the project execution plan.

u)  Using the guidance in DOE-STD-1073-93, Guide for Operational
    Configuration Management Program, discuss the System Engineer
    concept as it applies to oversight of safety systems. Specifically
    address the following areas of configuration management:

-   Assessment of system status and performance

-   Technical support for operation and maintenance activities

-   Technical support for DSA reviews

-   Document control

-   Change control

-   Design requirements

-   Assessments

### Assessment of System Status and Performance

As required by DOE O 433.1, Maintenance Management Program for DOE
Nuclear Facilities, systems and components within the configuration
management process must be monitored and tested periodically to
determine if they are still capable of meeting their design and
performance requirements. The process for performing this monitoring and
testing should be described in the maintenance implementation plan (MIP)
required by DOE O 433.1. DOE G 433.1-1, Nuclear Facility Maintenance
Management Program Guide for Use with DOE O 433.1, provides information
useful for developing and implementing this monitoring program.
Monitoring and testing may take the form of surveillance actions,
periodic in-service inspections, tests, and other monitoring of systems
and components to ensure safe and reliable operation of the facility. In
addition to observing direct results, derived results may include
reliability assessment, performance trending, and equipment aging
characteristics. Contractors should use the results of this monitoring
to identify and avoid inconsistencies between functional and performance
requirements identified in the design and actual capability of systems
and components. In addition, contractors should use trending of data to
detect degradation of equipment due to aging or other causes. By
performing periodic performance monitoring, contractors should verify
that selected systems and components continue to be able to perform
their intended functions (i.e., meet their design requirements).
Contractors should correct any deficiencies identified*.*

### Technical Support for Operation and Maintenance Activities

Management involvement in control of maintenance activities should
ensure that maintenance practices are effective in maintaining safe and
reliable facility operation. This control should extend to all facility,
contractor, and subcontractor personnel involved in maintenance
activities. Rigorous control of maintenance activities should be
directed toward achieving high-quality work performance, personnel
safety (including radiological protection), equipment and system
protection, and facility safety and reliability.

The work-control program should be based on administrative procedures
that address identification of needed work, planning and preparation for
work, establishment of conditions to perform work, conduct of work
activities, documentation of completed work, post-maintenance acceptance
of work, return-to-service procedures, review of completed work records,
control of temporary repairs, and control of non-facility contractor and
subcontractor personnel working in the facility.

A work-control program is an administrative method by which maintenance
activities are identified, initiated, planned, approved, scheduled,
coordinated, performed, and reviewed for adequacy and completeness. The
program should address

-   developing administrative procedures to describe the control of work
    from identification and planning through completion, review, and
    storage of historical data. Personnel, including key non-facility
    contractor and subcontractor personnel involved in the conduct and
    support of maintenance should be trained in using these procedures.

-   identifying the individuals/job titles responsible for performing
    various types of work, such as packing adjustments, equipment
    lubrication, and maintenance of health physics portable
    instrumentation.

-   using work request (WR) forms to control maintenance activities. A
    WR form (and/or work package) should be prepared and used to direct
    and document maintenance activities. This form should provide for
    documented review at the appropriate level. WR forms control
    maintenance activities by ensuring correct equipment energy
    isolation (e.g., personal locking devices in addition to operational
    control of lockout/tagout procedures), personnel safety, and the
    proper conduct of maintenance and post-maintenance tests (PMTs).

-   controlling troubleshooting to prevent unplanned repairs and
    unauthorized modifications.

-   reviewing requested work to ensure unauthorized modifications are
    not accomplished by the maintenance request.

-   setting goals for high-quality workmanship, safe work practices, and
    improved radiological protection, and for obtaining the support for
    these goals from maintenance personnel. A key factor in achieving
    these goals is work-site guidance and overview provided by
    maintenance supervisors. Monitoring to identify rework (maintenance
    that has to be repeated) can be effectively used to identify
    programmatic or qualification deficiencies.

-   documenting work accomplished and the results of PMTs, including the
    satisfactory return to service of the equipment or system.

-   reviewing WRs after the completion of maintenance to verify that the
    activity was satisfactorily completed in accordance with facility
    procedures and standards and to capture maintenance history data.

-   performing temporary repairs under the facility's temporary
    modification program.

-   establishing and maintaining the same policies and procedures for
    non-facility contractor and subcontractor personnel conducting
    maintenance on the site as facility personnel.

The work-control system should provide the data necessary to properly
plan and schedule maintenance activities. The work-control system also
provides a means of collecting facility maintenance data to be used for
failure analysis and maintenance history. The system used should be
comprehensive enough to fulfill these functions, yet simple enough to
function efficiently.

The maintenance organization should establish high standards for all
maintenance personnel engaged in supervising and performing maintenance
activities. These standards should ensure that work is conducted in
accordance with DOE, contractor, and facility policies and procedures.

Operational control of facility maintenance is facilitated by the proper
use of system status and lockout/tagout procedures, and by
communications between operations, maintenance, and other functional
groups at the work site. Lockout/tagout procedures should be
operationally controlled to maintain the safety envelope of
configuration controlled equipment and systems. Personal lockout/tagout
devices should be controlled by the maintenance organization for
individual personal safety while working on equipment under operational
configuration control. Configuration control is maintained by ensuring
that systems and equipment are restored to their original condition
following maintenance.

### Technical Support for DSA Reviews

Physical configuration assessments should be conducted at a specified
periodicity to establish confidence. Contractors should routinely review
the configuration of those systems performing vital safety functions
(safety SSCs). Additional systems of lesser importance should be
included at a lesser periodicity to ensure the breadth of the
configuration is being maintained adequately. Special reviews may be
required on an as needed basis, such as to verify input into a new DSA,
or when unusual or off-normal occurrences affecting the safety basis
systems result in a lack of confidence in the facility configuration or
in a concern that it has been compromised. Contractors should consider
scheduling reviews of the configuration of safety SSCs on an annual
basis on a schedule appropriate to support the annual update of the DSA.

### Document Control

Document control ensures that only the most recently approved versions
of documents are used in the process of operating, maintaining, and
modifying the nuclear facility. Document control helps ensure that

-   important facility documents are properly stored;

-   revisions to documents are controlled, tracked, and completed in a
    timely manner;

-   revised documents are formally distributed to designated users;

-   information concerning pending revisions is made available.

As controlled documents are updated to reflect changes to the
requirements and/or physical installation, the contractor must ensure
that

-   each updated document is uniquely identified, and includes a
    revision number and date;

-   each outdated document is replaced by the latest revision.

Contractors must determine what documents need to be controlled. They
also must define document owners who are responsible for developing and
revising the technical content of the documents and ensuring they are
maintained current. Document owners will also establish the schedules
for document revisions, distribution, and retrieval.

Documents to be controlled should include those documents that reflect
the facility's requirements, performance criteria, and associated design
bases. However, the number of documents that must be controlled should
be limited because of the resources required to properly control
documents.

DSAs, TSRs, documented design requirements, safety management plans, and
any other documents that are referenced by, or that support, the DSAs
should be controlled documents. Contractors should assess controlled
documents to determine if they need to be updated whenever changes are
made to the facility or activity configuration, the design requirements,
or other documentation that might impact them. Typical controlled
documents include the following:

-   DSAs

-   Authorization agreements and associated references

-   Safety management plans

-   Hazard controls, including TSRs

-   Documents that identify or define design requirements

-   Design specification and calculations

-   Accident analyses

-   Software data and manuals for operation and maintenance of critical
    software

-   Key procedures

-   Key drawings

-   Key vendor supplied documents

System design descriptions (SDDs) and other similar documents may
contain specific information about preventive and mitigative SSCs that
is too detailed to include in the DSA, but which facility personnel need
to understand design, operation, and maintenance of the facility,
activity, or operation. Whenever a change is initiated, the contractor
should also review the applicable SDDs to determine if they need to be
updated. The SDDs typically include the following:

-   Detailed design and operating descriptions

-   Diagrams, such as electrical schematics and piping and
    instrumentation diagrams

-   Load lists

After identifying which specific documents need to be controlled, the
following information on each document should be recorded in the
document databases to facilitate tracking and control:

-   Document type

-   Unique document number (document control number)

-   Document uses and priority

-   Document owner

-   Revision level

-   Current status (approved, draft, cancelled, superseded, etc.)

-   Information regarding pending changes

-   Other information needed for control and tracking, such as location
    and outstanding document change notices (DCNs)

This information should be retained in an easily retrievable manner.
Selected document information should also be entered into the
configuration management equipment database to establish a
cross-reference or link between configuration management systems and
components and the associated documents.

As new documents are generated, they should be reviewed for inclusion in
the controlled document database. One factor to consider in determining
if a document should be controlled is whether the new document supports
a configuration management SSC. The appropriate data on the document
should be entered into the controlled document database with the
appropriate data fields completed. The completeness and accuracy of the
controlled document database is essential to the control, tracking, and
retrieval functions of document control.

In order to ensure that the efforts and resources of document control
are appropriately focused, contractors should review the list of
controlled documents periodically and strive to consolidate and reduce
the volume of controlled documents.

### Change Control

Contractors must establish and use a formal change control process as
part of the configuration management process. The objective of change
control is to maintain consistency among design requirements, the
physical configuration, and the related facility documentation, even as
changes are made. The change control process is used to ensure that
changes are properly reviewed and coordinated across the various
organizations and among personnel responsible for activities and
programs at the nuclear facility.

Through the change control process, contractors must ensure that

-   changes are identified and assessed through the change control
    process;

-   changes receive appropriate technical and management review to
    evaluate the consequences of the changes;

-   changes are approved or disapproved;

-   waivers and deviations are properly evaluated and approved or
    denied, and the technical basis for the approval or the denial is
    documented;

-   approved changes are adequately and fully implemented, or the
    effects of the partial implementation are evaluated and accepted;

-   implemented changes are properly assessed to ensure the results of
    the changes agree with the expectations;

-   documents are revised consistent with the changes, and the revised
    documents are provided to the users.

### Design Requirements

The objective of the design requirements element of configuration
management is to document the design requirements. The design
requirements define the constraints and objectives placed on the
physical and functional configuration. The design requirements to be
controlled under configuration management will envelope the safety basis
and, typically, the authorization basis. Consequently, proper
application of the configuration management process should facilitate
the contractor's efforts to maintain the safety basis and the
authorization basis. Contractors must establish procedures and controls
for assessing new facilities and activities, and modifications to
facilities and activities, in order to identify and document design
requirements.

### Assessments

The quality assurance criteria of 10 CFR 830, subpart A, require DOE
contractors for nuclear facilities (including activities and operations)
to assess management processes and measure the adequacy of work
performance. Furthermore, the assessment criteria require the persons
performing the assessments

-   to have sufficient authority and freedom from line management

-   to be qualified to perform the assessments

The maintenance criteria of DOE O 433.1 also require periodic
assessments to verify the condition of systems and equipment.

Periodic assessments help ensure that work processes continue to
function properly, or that problems are identified, root causes are
determined, and problems are corrected. While contractors may perform
these assessments of the configuration management process separate from
other assessments, it may be more efficient to combine these assessments
with other periodic assessments of the activity. All or part of the
assessment of the adequacy of configuration management for an activity
may be integrated into broader management and performance assessments,
such as quality assurance, maintenance, or integrated safety management
assessments.

v)  Describe the quality assurance criteria of 10 CFR 830.120 which
    addresses the following:

-   Management

-   Performance

-   Assessment

Title 10 CFR 830.120 establishes quality assurance requirements for
contractors conducting activities, including providing items or services
that affect, or may affect, the nuclear safety of DOE nuclear
facilities. As part of the Quality Assurance Program (QAP), contractors
must conduct work in accordance with the following management,
performance, and assessment criteria:

-   Criterion 1 --- Management/Program. This criterion includes
    establishing an organizational structure, functional
    responsibilities, levels of authority, and interfaces for those
    managing, performing, and assessing the work; and establishing
    management processes, including planning, scheduling, and providing
    resources for the work.

-   Criterion 2 --- Management/Personnel Training and Qualification.
    This criterion includes training and qualifying personnel to be
    capable of performing their assigned work, and providing continuing
    training to personnel to maintain their job proficiency.

-   Criterion 3 --- Management/Quality Improvement. This criterion
    includes establishing and implementing processes to detect and
    prevent quality problems; identifying, controlling, and correcting
    items, services, and processes that do not meet established
    requirements; identifying the causes of problems and working to
    prevent recurrence as a part of correcting the problem; and
    reviewing item characteristics, process implementation, and other
    quality related information to identify items, services, and
    processes needing improvement.

-   Criterion 4 --- Management/Documents and Records. This criterion
    includes preparing, reviewing, approving, issuing, using, and
    revising documents to prescribe processes, specify requirements, or
    establish design; and specifying, preparing, reviewing, approving,
    and maintaining records.

-   Criterion 5 --- Performance/Work Processes. This criterion includes
    performing work consistent with technical standards, administrative
    controls, and other hazard controls adopted to meet regulatory or
    contract requirements using approved instructions, procedures, or
    other appropriate means; identifying and controlling items to ensure
    their proper use; maintaining items to prevent their damage, loss,
    or deterioration; and calibrating and maintaining equipment used for
    process monitoring or data collection.

-   Criterion 6 --- Performance/Design. This criterion includes
    designing items and processes using sound engineering/scientific
    principles and appropriate standards; incorporating applicable
    requirements and design bases in design work and design changes;
    identifying and controlling design interfaces; verifying or
    validating the adequacy of design products using individuals or
    groups other than those who performed the work; and verifying or
    validating work before approval and implementation of the design.

-   Criterion 7 --- Performance/Procurement. This criterion includes
    procuring items and services that meet established requirements and
    perform as specified; evaluating and selecting prospective suppliers
    on the basis of specified criteria; and establishing and
    implementing processes to ensure that approved suppliers continue to
    provide acceptable items and services.

-   Criterion 8 --- Performance/Inspection and Acceptance Testing. This
    criterion includes inspecting and testing specified items, services,
    and processes using established acceptance and performance criteria;
    and calibrating and maintaining equipment used for inspections and
    tests.

-   Criterion 9 --- Assessment/Management Assessment. This criterion
    includes ensuring that managers assess their management processes
    and identify and correct problems that hinder the organization from
    achieving its objectives.

-   Criterion 10 --- Assessment/Independent Assessment. This criterion
    includes planning and conducting independent assessments to measure
    item and service quality and the adequacy of work performance, and
    to promote improvement; establishing sufficient authority and
    freedom from line management for the group performing independent
    assessments; and ensuring that persons who perform independent
    assessments are technically qualified and knowledgeable in the areas
    to be assessed.

w)  Briefly discuss the maintenance management requirements as described
    in Life Cycle Assessment Management (DOE O 430.1).

Note: DOE O 430.1A was replaced by DOE O 430.1B, Real Property Asset
Management. However, the competencies contained therein may still be
applicable at some facilities. If the competencies are no longer
applicable at your facility, you can request an exemption from this
competency.

Per DOE O 430.1B, each site must have a maintenance program to maintain
each real property asset, including plant, property, and equipment, in a
condition suitable for its intended use. The maintenance program will
include condition assessments of real property assets, a work control
system, management of deferred maintenance, a method to prioritize
maintenance projects, and cost accounting systems to budget and track
maintenance expenditures. Configuration management of all assets in the
maintenance program will be consistent with the intent of DOE
STD-1073-93, Guide for Operational Configuration Management Program,
dated November 1992. In addition to the maintenance requirements of this
Order, sites with nuclear facilities must also comply with DOE O 433.1,
Maintenance Management Program for DOE Nuclear Facilities, dated June 1,
2001.

x)  Discuss the basic performance measurement tools used to monitor
    contractor performance.

The DOE approach outlined in Guidelines for Performance Measurement
calls for a six-step process. These six steps are addressed below.

### Step 1: Use a Collaborative Process

Develop the measurements using collaborative processes and include both
the people whose work will be measured and the people who will implement
important parts of the measurement process (if they are different). You
may want to have sponsors, internal customers, process owners, and
external customers review proposed performance objectives, measures,
expectations, and results. Obtain commitment to your measures and
measurement approach from your organization's top management. In order
for your measures to be taken seriously, it is extremely important that
top managers support your performance measurement process.

### Step 2: Describe Your Organization Processes

If you are developing measures for the first time, simply pick the one
that makes the most sense to you and start. If you already have a system
of measures, it is reasonable to look at other frameworks. They may help
you to improve your measures. Develop a flow process model or
input/output chart that defines your organization's main activities.

-   What are your main business processes?

-   What are the inputs to your organization and their sources?

-   What are outputs (e.g., products and services) from your
    organization?

-   Who are your customers (e.g., the users of the products and
    services)?

-   What are the desired outcomes for each business area?

-   What are the critical support functions (e.g., resource management)
    within your organization?

### Step 3: Design the Measurements

When you design performance measures, try to accomplish the following:

-   Identify information requirements from strategic plans. Design
    performance measures to demonstrate progress toward achieving the
    strategic and shorter-term goals laid out in your organization's
    strategic plan. This will identify your information needs. Make sure
    you have identified information to measure inputs, outputs, and
    outcomes for each business area. Identify some long-term, multi-year
    measures for purposes of monitoring long-term performance.

-   Understand the information requirements of organizations between you
    and the Secretary. Consider your organization's location within the
    DOE hierarchy, measures needed for reporting upward, and measures
    defined by parallel organizations, particularly those that use the
    same support organizations. Also consider measures in use by "best
    in class" organizations. If they fulfill one of your needs, adopt
    them.

-   Consider the impact of the measures that you define on organizations
    that support you. Carefully consider the resource impact of
    measurement implementation on support organizations. You should
    coordinate and establish standard definitions and reporting methods
    to ensure translation or integration of measures between and across
    multiple DOE organizations and organizational levels.

-   Select a few balanced measurements. Be selective in defining the
    actual measures to be generated. It is quite easy to measure too
    much. The process by which performance measurement data will be
    obtained should be defined at the same time the performance measure
    is defined. Developing a few particularly relevant measures is a
    good conceptual goal and is not easy to do. Balance (i.e., measuring
    multiple facets of your organization) assures that no aspect of the
    organization will suffer while another part is improved.

-   Avoid "yes/no" and milestone measures. Avoid "yes/no" performance
    measures, if possible. There is no valid calibration of the level of
    performance for this type of measure, and it does not motivate
    improvement. It is difficult to improve upon "pass" in a pass or
    fail measure.

### Step 4: Collect the Data

Note: This step is not covered here. Rather, it is covered in detail in
"Volume 4: Collecting Data to Assess Performance," of the PBM SIG's The
Performance-Based Management Handbook, available at
[http://www.orau.gov/pbm/pbmhandbook/Volume%202.pdf](http://www.orau.gov/pbm/pbmhandbook/Volume 2.pdf).

### Step 5: Use the Data

Note: This step is not covered here. Rather, it is covered in detail in
"Volume 5: Analyzing, Reviewing, and Reporting Performance Data," and
"Volume 6: Using Performance Information to Drive Improvement," of the
PBM SIG's The Performance-Based Management Handbook, available at
[http://www.orau.gov/pbm/pbmhandbook/Volume%202.pdf](http://www.orau.gov/pbm/pbmhandbook/Volume 2.pdf).

### Step 6: Continually Improve the Measurement Process

Expect to change your measures and measurement process to respond to
changing needs and priorities. Apply the concept of continuous
improvement to your measurement system to make sure your measures make
sense and measure the right things.

## Chemical Processing Personnel shall demonstrate a familiarity-level of knowledge of Software Quality Assurance relationships between the problems being addressed by safety analysis and design codes, the design requirements for the codes, and the components of the codes.

a)  Identify how functional requirements and applicability of safety
    analysis and design computer codes are defined, documented, and
    controlled relative to modeling and data assumptions, design
    constraints, sizing and timing conditions, and input/output
    parameters.

Functional requirements are defined using the following process:

-   An outline of the target system is developed and presented to the
    stakeholders for the purpose of soliciting their needs.

-   A first cut of the system overview diagram is created based on the
    outline statement. (Use case diagrams are useful for the purpose.)
    As this diagram is a very rough image, it should evolve over time.

-   Interviews with major stakeholders are conducted to solicit their
    needs.

-   Collected needs are defined.

-   Major functional requirements are identified.

-   Actors are identified.

-   Overall risks are analyzed.

-   Major quality requirements for each quality characteristic, such as
    safety, reliability, and usability, are identified. A quality model
    should be used for this purpose.

-   Required constraints and conditions, including total budget,
    delivery date, hardware and communication network environment, and
    available human resources are identified.

-   The system is refined into sub-systems, and the outline statement is
    re-defined. The system overview diagram and project description are
    refined based on the defined sub-systems.

For more information, refer to A Taxonomy of Safety-Related
Requirements, which can be found at
<http://www.sei.cmu.edu/community/rhas-workshop/firesmith.pdf>.

y)  Review a development project for safety analysis or design software.
    Explain how the problem being addressed by the software was
    translated into functional requirements, how the requirements were
    established and controlled, and how the code was reconciled with the
    original problem.

This is a performance-based competency. The qualifying official will
evaluate the completion of this competency.

## Chemical Processing Personnel shall demonstrate a familiarity-level of knowledge of Software Quality Assurance functional interfaces between safety system software components and the system-level design.

a)  Identify how system-level requirements are established and then
    assigned to hardware, software, and human components of a digital
    instrumentation and control system.

The performance or functional requirements of the process system are
defined first. From these, the control requirements can be developed.
Once the controlled parameters and items are identified, control
elements and methods can be identified and selected. This must include
the sensor or detector response time in the system, the lag time for the
control system (analog, digital, or manual) to respond to the detector
and signal the control element, the lag time for the control element to
operate, and the system response to action by the control element. These
factors influence the type of control system selected. Digital systems
have the advantage that the mathematical control algorithms can be
changed without major changes to the hardware. Digital systems can also
be used to provide software interlocks without having to route
additional wiring and sensors or add relays. Once the control
requirements and methods are established, the control elements can be
assigned to the process control points. The measurement methods may also
impact the lag storage required for process material. As an example, if
the key parameter, say impurity levels, can only be measured with a
24-hour response time, a day or two lag storage is needed, and even the
fastest digital control system is only an operator aid (i.e., the
control system holds until the operator tells it to do something vs. the
operator re-aligns the valves).

To use automated control, a logic diagram is required for all but the
simplest control systems. This will include sensor input, operator
input, control and process modeling, and sensor output. In a digital
system, the hardware either senses, acts, or amplifies and carries
signal. The software responds to sensors and operator input, displays
status to the operator(s), and sends signals to control elements. The
system-level requirements will identify those functions that must occur
automatically, the alarms needed for operator intervention, and the
condition the system should assume in an alarm condition. Failure modes
of components must also be identified and perhaps specified (e.g., does
a valve fail open, closed, last on loss of power or loss of air).

z)  Identify the typical requirements that define functional interfaces
    between safety system software components and the system-level
    design, as described in standards such as ANSI/IEEE 830, IEEE Guide
    to Software Requirements Specifications and IEEE 7-4.3.2, Standard
    Criteria for Digital Computers in Safety Systems of Nuclear Power
    Generating Stations.

System-level requirements will drive the functional software
requirements specifications. These will include

-   performance of the intended control and alarm functions as
    identified from the process or system requirements;

-   detection of incorrect hardware operation, and response to the
    detected condition (e.g., supervised circuits, flow verification
    after a valve opens, etc.);

-   integrity, security, and configuration control issues (e.g.,
    attempted incorrect operation, failure of operator to respond to
    alarm condition);

-   human interface considerations (e.g., deadman circuits, display
    requirements, redundant input or two-key requirements);

-   system response to fault conditions (e.g., voting logic, go to safe
    shutdown if independent systems disagree, etc.);

-   the ability to tolerate, detect, and recover or safely shut down
    from fault or abnormal conditions.

    Safety system software in this context is an integral part of the
    control system, and must be included in the hazards analysis and
    detailed safety analysis.

a)  Identify the specific records that must be maintained and the
    requirements for maintaining these records to document the
    development of safety system software.

Records that must be maintained include the following:

-   Project management plan

-   Software quality assurance plan

-   Risk assessment and risk management plan

-   Procurement and supplier management and quality plan (if applicable)

-   Software requirements identification documents

-   Functional requirements

-   Software requirements specification

-   Hazards analysis and safety analysis documentation

-   Design, engineering, and development records

-   Verification and validation plans, execution, and results

-   Record of discovered problems and non-conformances, corrective
    action taken, and verification that corrective action was effective

-   Training and user manuals

# Selected Bibliography and Suggested Reading

10 CFR 830, "Nuclear Safety Management." January 2006.

[]{.mark}

29 CFR 1910, "Occupational Safety and Health Standards." July 2005.

29 CFR 1910.38, "Emergency Action Plans." July 2005.

29 CFR 1910.119, "Process Safety Management of Highly Hazardous
Chemicals." July 2005.

29 CFR 1910.120, "Hazardous Waste Operations and Emergency Response."
July 2005.

29 CFR 1910.1200, "Hazard Communication." July 2005.

29 CFR 1926, "Safety and Health Regulations for Construction." July
2005.

40 CFR 300, "National Oil and Hazardous Substances Pollution Contingency
Plan." July 2005.

40 CFR 300.150, "Worker Health and Safety." July 2005.

American Institute of Chemical Engineers, Center for Chemical Process
Safety. *Essential Practices for Managing Chemical Reactivity Hazards*.
2003.

American Institute of Chemical Engineers, Center for Chemical Process
Safety. *Reactive Material Hazards --- What You Need to Know.* 2001.

American Institute of Chemical Engineers, Center for Chemical Process
Safety. *Guidelines for Chemical Reactivity Evaluation and Application
to Process Design*. 1995.

ANSI/IEEE 830-1993. *IEEE Guide to Software Requirements
Specifications.* American National Standards Institute, 1993.

Canadian Centre for Occupational Health and Safety. *Dangerously
Reactive Liquids and Solids and Their Hazards*. August 13, 2004.

Environmental Protection Agency, Chemical Emergency Preparedness and
Prevention Office. Chemical Safety Alert EPA 550-F-01-010, *Chemical
Accidents from Electric Power Outages.* September 2001.

Environmental Protection Agency, Chemical Emergency Preparedness and
Prevention Office. Chemical Safety Alert EPA 550-F-97-002e, *Fire Hazard
from Carbon Adsorption Deodorizing Systems.* May 18, 1997.

Environmental Protection Agency, Chemical Emergency Preparedness and
Prevention Office. Chemical Safety Alert EPA-F-99-006, *Use Multiple
Data Sources for Safer Emergency*. June 1999.

European Commission, Industrial and Materials Technologies Programme.
*Thematic Network on Hazard Assessment of Highly Reactive Systems
(HarsNet).* [http://www.harsnet.net](http://www.harsnet.net/).

Health & Safety Executive. Contract Research Report No. 100/1996, *Safe
Disposal of Vented Reacting Fluids*. 1996.

ISSS 7-4.3.2, *Standard Criteria for Digital Computers in Safety Systems
of Nuclear Power Generating Stations.* 2003.

Mary Kay O'Connor Process Safety Center. *Reactive Chemicals.*

U.S. Congress. *Comprehensive Environmental Response, Compensation, and
Liability Act*. 1980.

U.S. Congress. *Superfund Amendment Reauthorization Act*. 1986.

U.S. Department of Energy. DOE Guide 433.1-1, *Nuclear Facility
Maintenance Management Program Guide for Use with DOE O 433.1*.
September 5, 2001.

U.S. Department of Energy. DOE Order 413.3, *Project Management for the
Acquisition of Capital Assets.* March 28, 2003.

U.S. Department of Energy. DOE Order 420.1A, *Facility Safety*. May 20,
2002.

U.S. Department of Energy. DOE Order 425.1C, *Startup and Restart of
Nuclear Facilities*. March 13, 2003.

U.S. Department of Energy. DOE Order 430.1B, *Real Property Asset
Management.*\
September 24, 2003.

U.S. Department of Energy. DOE Order 433.1, *Maintenance Management
Program for DOE Nuclear Facilities*. June 1, 2001.

U.S. Department of Energy. DOE-STD-1027-92, *DOE Standard Hazard
Categorization and Accident Analysis Techniques for Compliance with DOE
Order 5480.23, Nuclear Safety Analysis Reports*. 1997.

U.S. Department of Energy. DOE STD-1073-93, *Guide for Operational
Configuration Management Program.* November 1992.

U.S. Department of Energy. DOE-STD-3009, *Preparation Guide for U.S.
Department of Energy Nonreactor Nuclear Facility Documented Safety
Analyses*. March 2006.

U.S. Department of Energy. DOE-STD-3011, *Guidance for Preparation of
Basis for Interim Operation (BIO) Documents.* November 1994.

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