GabrielS.

Gusmo
Dr.Tam
CHE175AProblemSet1
Duedate:02/02/12

ChemicalProcessDesignProblemSet1
1. A plant employs 1500 fulltime workers in a process with a FAR of 5. How many industrial
relateddeathsareexpectedperyear?
Answer:
FARisanacronymforFatalAccidentRatewhichconsistsinthenumberoffatalitiesbasedon1000
employeesactivetheirwholelifetimes;accordingtoCrownlandLovar
1
,FARisdefinedas:
FAR =
Numbcr o Fotolitics 1u
8
Iotol numbcr o bours workcJ by oll
cmployccs Juring pcrioJ co:crcJ

Thefatalityrate(FR)comprehendsthenumberofexpectedfatalitiesperpersonperyear.
FR =
Numbcr o Fotolitics pcr ycor
Iotol numbcr o pcoplc in
oplicoblc populotion

Assumingthatafulltimeworkerworks8hoursperdayand300daysperyear,itfollowsthat:
FAR =
S Jcotbs
1uu,uuu,uuu b

FR = FAR _8
bours
Joy
Suu
Joy
yr
]
1
workcr
= 1.2 1u
-4
Jcotb
workcr yr

InJustriol rclotcJ Jcotb pcr ycor = FR 1Suu workcrs = u.18
Jcotb
yr

1
Seeref.I
GabrielS.Gusmo
Dr.Tam
CHE175AProblemSet1
Duedate:02/02/12

2. Estimatetheflashpointofasolutionof50mol%waterand50mol%ethanol.
Answer:
FromPerrysChemicalEngineeringHandbook,7
th
edition,thevaporpressureofethanolandwater
fromDIPPRmethodaregivenby:
P
up
(I|K]) = exp _C
1
+
C
2
I
+ C
3
ln(I) + C
4
I
C
S
] |Po]
Table1.1ParametersforDIPPRVaporPressureEquation
2

Substance C
1
C
2
C
3
C
4
C
5

Water 73.649 7258.2 7.3037 4.165310

6
2
Ethanol 74.475 7164.3 7.327 3.134010
6
2

Giventheextremelystrongintermolecularhydrogenbondinteractionbetweenwaterandethanol
the nonideal mixture shall be described through Gamma/Phi approach with fugacity coefficient
for the gas phase, which may be taken as one due to the low pressure considered, and activity
coefficient for the liquid phase calculated from simple Margules equation with parameters taken
fromPerrysHandbook.
ln(
1
) = |A

12
+ 2(A

21
- A

12
)x
1
] x
2
2

ln(
2
) = |A

21
+ 2(A

12
- A

21
)x
2
] x
1
2

Table1.2MargulesEquationParameterforVLEofEthanol(1)andWater(2)
3

Parameter Value
A

12
1.6022
A

21
1.493
Given that it is a binary equimolar mixture and the parameters were given, both activity
coefficientscanbecalculated:
Table1.3ActivityCoefficientofEthanol(1)andWater(2)inMixture
Parameter Value

1
1.22

2
0.7947

2
fromPerryetal.,Table26
3
FromPerryetal.,Table132
GabrielS.Gusmo
Dr.Tam
CHE175AProblemSet1
Duedate:02/02/12

Formixtureswithonlyoneflammablecomponent,likewaterethanol,theflashpointtemperature
of the mixture is situated at the temperature in which the flammable component vapor pressure
inthemixtureisequaltoitsvaporpressureaspurecomponentatitsflashpoint.
From anhydrous ethanol MSDS sheet
4
from PHARMCOAAPER consulted at <www.msds.com>
website,itsflashpointis14Cclosedcup.Atflashpoint,14C(287.15K),ethanolvaporpressure
isgivenfromDIPPRequation.
P
cthunoI
PP
(287.1SK) = 4.u76 kPo
ThroughtheGamma/PhiapproachforVLEatlowpressures:
P

up
x

= P y

p
cthunoI
= P y
ctunoI
= P
cthunoI
up
(I) x
cthunoI
1.22
Forequimolarmixture,lettingpartialvaporpressureofethanolequaltoitsflashandsolvingDIPPR
equationnumerically(throughMathcad15
5
)fortemperature,itleadsto:
root o _P
cthunoI
up
(I) -
4.u76 kPo
u.S 1.22
_ = 29S.2S K = 22.u8C
3. EstimatetheLFLandtheUFLofthefollowingmixtureofhexane(1%),methane(1%),ethylene
(1%),andair(97%).
Answer:
As there are only nonpolar components being regarded and their intermolecular interaction are
farduetoonlymutualinduction,theidealequilibriumhypothesisshallestimatetherealmixture
behavior. From Daniel et al.
6
, the Lower Flammable Limit for the combustible components are
givenbelow.
Table1.4LowerandUpperFlammableLimitandConcentrationofComponents
Component
Concentration
(vol.%)
Molefractionon
combustiblebasis
LFL
(vol.%)
UFL
(vol.%)
Hexane 1 1S 1.2 7.S
Methane 1 1S S.S 1S
Ethylene 1 1S S.1 S2.u
Air 97

4
MaterialSafetyDataSheetfromPHARCOAAPER,seeref.II
5
PTCMathcad15,seeref.III
6
Reference1,AppendixB
GabrielS.Gusmo
Dr.Tam
CHE175AProblemSet1
Duedate:02/02/12

KnowingthatMolefractiononcombustiblebasisisgivenbydividingthenumberofmolesofthe
respective combustible specie by the total number of moles of combustible species. Something
that can be done easily if assuming ideal gas behavior; where the volume concentration
correspondstothemoleconcentration.Thisassumptionshouldestimatetherealbehaviorofthe
gasphasebecauseinthiscaselowpressures(1atm)arebeingconsidered.Consequently,through
LeChateliersPrinciple,itcomesthat:
(IFI)
mx
=
1
(y

IFI

)
n
=1

(IFI)
mx
= _
1
S
_
1
1.2
+
1
S.S
+
1
S.1
]_
-1
= 2.2S% :ol. totol combustiblcs.
Likewise,theUpperFlammableLimit(FLF)forthemixturecanbedenotedasfollowing.
(uFI)
mx
=
1
(y

uFI

)
n
=1

(uFI)
mx
= _
1
S
_
1
7.S
+
1
1S
+
1
S2
]_ = 12.97% :ol. totol combustiblcs.
4. Do some research, the links to California and Federal regulations have been provided in
lectureclass.Citeyoursourcesofinformation.
a. AccordingtotheDepartmentofTransportationOfficeofHazardousMaterialSafety,
howmanyincidentsoccurredin2011forallmodesofthetransportationprocess?
Answer:
From data available in Hazmat Intelligence Portal
7
redirected from PHMSA, U.S. Department of
TransportationPipelineandHazardousMaterialsSafetyAdministrationwebsite
8
,therehappened
atotalof14,491accidentsrelatedtotransportationsprocess,amongdifferentphasessuchas:in
transit,intransitstorage,loadingandunloading.

7
From<https://hip.phmsa.dot.gov>;accessedin01/31/12,at10:45p.m.
8
From<http://www.phmsa.dot.gov/hazmat/library/datastats/incidents>;accessedin01/31/12,at10:45
p.m.
GabrielS.Gusmo
Dr.Tam
CHE175AProblemSet1
Duedate:02/02/12

Table1.5IncidentsforAllModesoftheTransportationProcessinCalifornia,2011*
Tianspoitation
Phase
Inciuents Bospitalizeu
Non
Bospitalizeu
Fatalities Bamages
In Transit S,718 1S S8 9 $89,S28,66S
In Transit Storage SSu 2 6 u $88S,8u7
Loading 2,747 u 22 2 $8SS,719
Unloading 7,476 1u S8 u $17,8S1,19u
Grand Total 14,491 25 124 11 $109,079,379
*Source:HazmatIntelligencePortal,U.S.DepartmentofTransportation.Dataasof2/1/2012
Figure1.1IncidentsbyTransportationPhaseinCalifornia,2011*

*Source:HazmatIntelligencePortal,U.S.DepartmentofTransportation.Dataasof2/1/2012
Through the chart, is noteworthy that most accidents occur in transit or when unloading the
material; hence, is presumable that disturbs during transit and lack of attention when unloading
maybecausesoftheseincidents.

GabrielS.Gusmo
Dr.Tam
CHE175AProblemSet1
Duedate:02/02/12

b. Provideinformationonhydrogensulfide(H2S)regarding:
Answer:
Following data are from MSDS datasheet from the Hardy Research Group, Department of
Chemistry,TheUniversityofAkron
9

i) Physical State and Appearance: Colorless gas with strong odor of rotten eggs. Fatigues
thesenseofsmellwhichcannotbecountedontowarnofthecontinuedpresenceof
thegas.
ii) PhysicalDangers:Compoundisheavierthanairandmaytravelaconsiderabledistanceto
source of ignition and flash back. It forms explosive mixtures with air over a wide
range.
iii) Chemical Dangers: Reacts explosively with bromine pentafluoride, chlorine trifluoride,
nitrogen triiodide, nitrogen trichloride, oxygen difluoride, and phenyl diazonium
chloride. When heated to decomposition, it emits highly toxic fumes of oxides of
sulfur. Incompatible with many materials including strong oxidizers, metals, strong
nitric acid, bromine pentafluoride, chlorine trifluoride, nitrogen triiodide, nitrogen
trichloride,oxygendifluorideandphenyldiazoniumchloride.
Databelowarefromthe UnitedStatesDepartment ofLabor,OccupationalSafetyand Health
Administration,OSHA
10

iv) TLV,STEL(assumingREL),PEL(andincludingIDLH):
American Conference of Governmental Industrial Hygienists (ACGIH) Threshold Limit
Value(TLV):
(TLVTWA):1ppm,14mg/m
(TLVSTEL):15ppm,21mg/m

9
From<http://ull.chemistry.uakron.edu/erd/Chemicals/8000/6567.html>;accessedon01/31/12,at11:39
p.m.;seeref.IX.

10
FromOSHA:<http://www.osha.gov/dts/chemicalsampling/data/CH_246800.html>;accessedon
02/01/12,at12:55a.m.,seeref.VIII.

GabrielS.Gusmo
Dr.Tam
CHE175AProblemSet1
Duedate:02/02/12

OSHAPermissibleExposureLimit(PEL):
General Industry:(PELC): 20 ppm (ceiling) with the following exception: if no
other measurable exposure occurs during the 8hour work shift, exposures
may exceed 20 ppm, but not more than 50 ppm (peak), for a single time
periodupto10minutes.
ConstructionIndustry(PELTWA):10ppm,15mg/m
Maritime(PELTWA):10ppm,15mg/m
National Institute for Occupational Safety and Health (NIOSH) Recommended
ExposureLimit(REL):
Limit(REL):10ppm,15mg/mCeiling(10Minutes)
NIOSHImmediatelyDangeroustoLifeorHealthConcentration(IDLH):100ppm
(IDLH):100ppm
v) EffectsofShortTermExposure:
The substance is irritating to the eyes and the respiratory tract. The substance may
causeeffectsonthecentralnervoussystem.Exposuremayresultinunconsciousness.
Exposure may result in death. Inhalation of gas may cause lung edema. The effects
maybedelayed.Medicalobservationisindicated.Rapidevaporationoftheliquidmay
causefrostbite.
vi) EffectsofLongTermExposure:
So far studies were not reliable
11
and there is no evidence whether longterm
exposuremaycauseanyharm.
Longterm H2S exposure has mainly been associated with nervous and respiratory
system and eye effects. However, controversy exists as to whether or not longterm
exposure to H2S causes any significant health effects. The disagreement centers on
the quality of the research and the nature of someof the reported symptoms, which
includefatigue,headache,dizziness,irritability,andlossofappetite.Thesesymptoms
arenotspecifictoH2Sexposureandcouldbeduetoanumberofothercauses.

11
FromCCOHS:<http://www.ccohs.ca/products/databases/samples/cheminfo.html>,accessedin02/01/12,
at01:25a.m.;seeref.VII.
GabrielS.Gusmo
Dr.Tam
CHE175AProblemSet1
Duedate:02/02/12

There are a few studies that have evaluated the potential effects of longterm
environmental exposure to H2S. These studies are not reviewed here, since they are
limited by factors such as concurrent exposures to many other chemicals, and self
reportingbiases.
c. WhattypesofworkersarecoveredunderOSHA?(Forexample:privatesector
workers,stateandlocalgovernmentworkers,federalgovernmentworkers,self
employedworkers,etc.?)
Answer
12
:
Private Sector Workers: As OSHA covers all 50 states, the District of Columbia and other
U.S. jurisdiction directly or through state program state programs approved by its
requirements, most employees in the United States are covered by its laws; in addition,
stateprogramsconcerninghealthyandsafetymustbehoweveraseffectiveastheFederal
OSHAprogram.
StateandLocalGovernmentWorkers:NotcoveredbyFederalOSHA,buttheyarecovered
by OSH Act protections if the state where they work has a program approved by OSHA.
States in the U.S. that have OSHA approved programs that cover employees of public
sector are: Illinois, Connecticut, New Jersey, New York, and the Virgin Islands; moreover,
privatesectorworkersinthefourstatesstatedareunderFederalOSHAcoverage.
FederalGovernmentWorkers:TheUnitedStatesPostalService,USPS,iscoveredbyOSHA.
American federal agencies have to provide safety and health programs at the same level
of precaution OSHA offers. Although feral employees are not covered by OSHA, their
requirementsregardinglawscomprisedbyOSHAareattended.
Selfemployed people, immediate family relatives of farm employers that do not employ
outside employees and Workplace Hazards regulated by another Federal agency (for
example,theMineSafetyandHealthAdministration,theFederalAviationAdministration,
theCoastGuard)areNOTcoveredbyOSHA.

12
FromOSHA:<http://www.osha.gov/workers.html>,accessedin02/01/12,at01:41a.m.

GabrielS.Gusmo
Dr.Tam
CHE175AProblemSet1
Duedate:02/02/12

5. AfterreadingthetwoarticlesfromtheSupplementalReadingssectionintheCourseMaterials
folderofiLearn,answerthefollowingquestions.
a. WhatisLOPA?SIL4?
Answer:
InFrontEndEngineeringPhase
Asthehazardandoperability(HAZOP),LOPA,whichisanacronymforLayerofProtectionAnalysis,
is one of the current tools that aid a professional identifying Inherently Safer Design, ISD,
necessities and alternatives during the FrontEnd Engineering and Design, FEED, stage. Based on
equipment reliability statistics, through LOPA, it is possible to estimate the probability of an
unexpecteddisturbeventtohappenandthecapabilityofdifferentlayersofprotectionsystemto
damp its consequences. By analyzing the expected frequencies of disturbs and its modeled
projected consequences, the designer should be able to decide where to modify the process;,
either by locating the sources of disturbs and reducing its likeability to happen or changing the
processdownstreamsothattheconsequencesoftheeventsarediminished.
InDetailedDesignPhase
At this point of the design process more information regarding process parameters and variables
thatshouldbeconcernedasHAZOPfocusareavailable;consequently,specificpartsoftheproject
where unexpected events, of considerably danger consequences may happen, becomes more
obvious. However, as process matures, it turns more difficult to undertake great modifications,
and applications of LOPA in this stage generally focus on defining the necessary Safety Integrity
Level,SIL,basedonthenecessityornotofdecreasingthelikelihoodorprobabilityofaneventto
happen to a tolerable level. LOPA does not provide any concernment about modifications in the
process; nonetheless, it is an indicator that redesigning the process through Inherently Safer
Design modifications may be more feasible than just accreting redundant safety instrument
systems, SIS. As the requirements on safety increases, so does SIL, and it implies including more
expensive and robust safety instrument system; for instance, at SIL4 are comprehended nuclear
facilitiessothat,dueitscomplexitiesandpotentialdangerousness,thereliabilityrequiredinterms
of process safety are far beyond the level that general chemical Industries requires. Concluding,
LOPA is a tool that indicates whether ISD modifications in the process are worth or when simply
addingSISismorecosteffective.

GabrielS.Gusmo
Dr.Tam
CHE175AProblemSet1
Duedate:02/02/12

10

b. WhatchangesdidDuPontimplementtotheirprocessofinsecticideproductionafter
theBhopal,Indiaincident?
Answer:
DuPonthasdeployeddifferentmodificationsinitsupplychain,developedanewreaction,andalso
changed one of the reactants source to a more stable one in order to minimize likeability of
happeninganunexpectedevent,suchastheoneinBopal,intheirinsecticideproductionprocess.
Through Inherently Safer Design modifications, based on substitution and minimization,
accompanied by researches, they refrained from storing huge amounts of a potential harmful
reactant, named MIC (methyl isocyanate), whereas they have substituted MIC for other less
hazardous raw material that, through a new reactor they have developed, could be shifted into
MICinsituandthenitcouldproceedinthereactionchainuntiljointheinsecticidescomposition.
Consequently, SIL has decreased, given the less harmful characteristic of the new raw material
thatnowcanbetransportedwithfewerrequirementsofsafetyinstrumentsystems.
6. References
I. Crowl, Daniel A. and Louvar, Joseph F.; Chemical Process Safety: Fundamentals with
Applications.2nded.;2002byPrenticeHallPTR.
II. Material Safety Data Sheet from PHARCOAAPER, Ethyl Alcohol 200 proof
USP/ACS/EP/Grain/Synthetic/Kosher; consulted at <www.msds.com> at 10:43 p.m.,
January30,2012.
III. Mathcad15.0Copyright2010ParametricTechnologyCorporation.
IV. Edwards,V.H.andChosnek,J.;MakeYourExistingPlantInherentlySafer;American
InstituteofChemicalEngineers(AIChE),January2012
V. Maher, S. T.; Norton, K. D. and Surmeli, S.; Design an In.herently Safer Plant;
AmericanInstituteofChemicalEngineers(AIChE),January2012.
VI. CenterforDiseaseControlandPrevention;<http://www.cdc.gov/>.
VII. CCOHS, Canadian Centre for Occupational Health and Safety
<http://www.ccohs.ca/products/databases/samples/cheminfo.html>.
VIII. HealthAdministration,OSHA,<http://www.osha.gov/>.
IX. HordeNet, Hardy Research Group Department of Chemistry, the University of Akron;
<http://ull.chemistry.uakron.edu/>.