GE Text Solutions Manual

Solutions Manual
for
Green Engineering:
Environmentally Conscious Design of Chemical Processes
David R. Shonnard
Michigan Technological University
David T. Allen
University of Texas at Austin
ther Authors
!red Arnold
Scott Prothero
U.S. Environmental Protection Agency
"irsten Rosselot
Process Profiles
Prentice #all$ %&&'
Contents
I. An Introduction to Environmental Issues, page 3
II. Risk Concepts, page 6
III. Environmental Law & Regulations: rom End!o!"ipe to "ollution, page #$
I%. Roles & Responsi&ilities o C'emical Engineers, page #3
%. Evaluating Environmental (ate: Approac'es )ased on C'emical *tructure, page #+
%I. Evaluating E,posures, page -.
%II. /reen C'emistr0, page 36
%III. Evaluating Environmental "erormance 1uring "rocess *0nt'esis, page 2#
I3. 4nit 5perations & "ollution "revention, page 26
3. (lows'eet Anal0sis or "ollution "revention, page +2
3I. Evaluating t'e Environmental "erormance o a (lows'eet, page 66
3II. Environmental Cost Accounting, page .+
3III. Lie!C0cle Concepts, "roduct *tewards'ip & /reen Engineering, page .7
3I%. Industrial Ecolog0, page 73

-
Cha(ter '. An )ntroduction to Environmental )ssues

'. Electric *ehicles: Effects on )ndustrial Production of !uels
8'ere are two main points to &e addressed &0 t'is 9uestion o electric ve'icles versus conventional
gasoline!powered ve'icles: #: w'at are t'e c'anges likel0 to occur in industrial uels production, and -:
w'at are t'e likel0 c'anges in environmental impact as a result o t'is c'ange due to com&ustion o t'ese
uels. 8o address t'e irst 9uestion, inormation is needed on t'e average mi, o energ0 sources in t'e
4nited *tates or electricit0 generation. According to t'e 1epartment o Energ0 ;15E: in a report
</REE8 #.+ = 8ransportation (uel!C0cle >odel? ;'ttp:@@www.transportation.anl.gov@ttrdc@greet@:, t'e
average mi, is +3.7A coal, #.$A oil, #2.6A natural gas, #7A nuclear, and #-.3A ot'ers ;'0droelectric,
wind, solar, etc.:. 8'us, i electric ve'icles replace conventional gasoline!powered ve'icles or personal
transportation, uels production and import would switc' rom petroleum and petroleum products to more
coal, natural gas, nuclear, and ot'er. 8'ere would &e more mining activities or t'e e,traction o coal and
uranium and less reliance on oreign oil. 8'e second 9uestion, regarding t'e environmental impacts o t'e
com&ustion processes to suppl0 t'e electricit0, is more complicated. A stud0 using t'e /REE8 model
indicate t'at on a per mile traveled &asis comparing electric ve'icles compared to conventional gasoline!
powered ve'icles, C5
-
emissions would decrease &0 a&out -+A, volatile organic compounds ;%5Cs: and
C5 decrease &0 a&out 7$A, B5, would increase &0 a&out 6$A, and *5
-
would increase &0 a&out -2$A.

%. Glo+al Energy ,alance: -o Atmos(here
a: Energ0 )alance:
<Rate o *olar Energ0 A&sor&ed? C <Rate o Inrared Energ0 Emitted?
;#!A: S R
E
-
C E 2 R
E
-

E
(1 A)S
4
(1.3)(1,360Datts / m
2
)
4
238 Datts/ m
2
&: /lo&al Average *urace 8emperature:
E T
4

T
E

1
]
1
1/ 4
238Datts / m
2
5.67 10
8
Datts @ ;m
-
E
2
:

1
]
1
1/ 4
254.5E
Compared to -7$ E, t'e actual average surace temperature. 8'e calculated value is low &ecause o t'e
green'ouse eect was omitted.

.. Glo+al Energy ,alance: /ith a Greenhouse Gas Atmos(here
At t'e eart'Fs surace, a radiation &alance re9uires t'at
;irradiance in C irradiance out:
3
$.6E G y C x
w'ile or t'e atmosp'ere la0er, t'e radiation &alance is
E G x C $.6E G -y G .-x
3. *olving t'ese e9uations simultaneousl0 or y and x results in
y
.82
1.2
E
.82
1.2
(238W / m
2
) 162.6W / m
2
x 1.583 E 1.583(238W / m
2
) 376.8W / m
2
2. *urace temperature:
x 376.8W / m
2
T
4
T
x

1
]
1
1/ 4
376.8W / m
2
5.67 10
8
W / (m
2
K
4
)

1
]
1
1/ 4
285.5 K
Atmosp'ere temperature:
y .8 T
4
T
y
.8

1
]
1
1/ 4
162.6W / m
2
(.8)(5.67 10
8
W / (m
2
K
4
))

1
]
1
1/ 4
244.7 K
+. In order or t'e glo&al average surace temperature o t'e eart' to rise &0 # HC a&ove t'e value
calculated in part & ;-7+.+-E:, t'e inrared a&sor&tivit0 would need to increase to $.7#66 rom $.7$.

0. Glo+al Car+on Dio1ide Mass ,alance
a: A mass &alance or C5
-
at t'e eart'Is surace is
Accumulation o C5
-
in atmosp'ere C rate o C5
-
release rom surace !
rate o C5
-
removal &0 surace
Accumulation o C5
-
in atmosp'ere ;metric tons C@0r: C ;6$G6G#.6: ! ;6$G-G.+G#.7:
C 3.3 metric tons C@0r
C

(3.310
9
metric tons@ 0r)
44gC5
2
12gC

_
,

10
3
kg
metric ton

_
,

+1.2110
13
kgC5
2
@ 0r
6. G#$A c'ange in emissions rom uel com&ustion is G.6A or a total o 6.6A
Accumulation o C5
-
in atmosp'ere ;metric tons C@0r: C ;6$G6.6G#.6: ! ;6$G-G.+G#.7:
2
C

(3.910
9
metric tons @ 0r)
44gC5
2
12gC

_
,

10
3
kg
metric ton

_
,

+1.4310
13
kgC5
2
@ 0r
G#A c'ange in emissions rom release &0 microorganisms is G.6A or a total o 6$.6A
Accumulation o C5
-
in atmosp'ere ;metric tons C@0r: C ;6$.6G6G#.6: ! ;6$G-G.+G#.7:
C

(3.910
9
metric tons @ 0r)
44gC5
2
12gC

_
,

10
3
kg
metric ton

_
,

+1.4310
13
kgC5
2
@ 0r
.. Rate o c'ange or C5
-
concentration in atmosp'ere ;ppm@0r:
C'ange in num&er o moles C5
-
rom part a C

(1.21 10
13
kgC5
2
@ 0r:
#$
3
g
kg

_
,

1mole C5
2
22 gC5
2

_
,

2.75 10
14
moles C5
2
@ 0r
C'ange in mole raction ;ppm: o C5
-
C

2.7510
14
molesC5
2
@ 0r
1.510
20
moles air

_
,

1ppm
#$
!6
molesC5
2
moles air

_
,

1.83ppm@ 0r
8'is rate o c'ange compares well wit' t'e o&served rate o c'ange o $.+A@0r, w'ic' at t'e current
concentration o C5
-
is ;.$$+:;36$ ppm: C #.7$ ppm@0r.
7. 8'e rate o C5
-
accumulation would decrease i t'e processes o C5
-
ertiliJation and orest growt'
were en'anced &0 a uture glo&al temperature rise. 5n t'e ot'er 'and, t'e rate o C5
-
accumulation
would increase i t'e processes o C5
-
release were accelerated, or e,ample, &0 micro&ial
meta&olism in soil.

2. 3one De(letion Potential of Su+stitute Refrigerants
A discussed in c'apter #, &romine is a muc' more potent oJone depletion su&stance compared to c'lorine
on a per!atom &asis. (luorine is t'oug't to 'ave no adverse oJone depletion eects. 8'ereore,
su&stituting luorine or c'lorine on alternative rerigerants would 'elp solve t'e oJone depletion pro&lem.
5n t'e ot'er 'and, luorine on '0drocar&on rerigerants is a potent green'ouse gas and luorinated
compounds 'ave &een ound to accumulate in t'e &od0 at o animals as ar awa0 as t'e arctic, well awa0
rom an0 known sources o t'ese compounds. Apparentl0 t'e persistence o t'ese luorinated compounds
com&ined wit' atmosp'eric transport over long distances creates e,posure to t'ese remote creatures.

+

Cha(ter %. Ris4 Conce(ts

'. Ris4 of Death in Automo+ile Accidents
De can e,press t'e risk o deat' in an automo&ile accident in t'e conte,t o c'emical risk as presented in
C'apter -.
Risk o 1eat' &0 Car Accident C ;E,posure: ;KaJard:
In t'is e9uation, risk is t'e num&er o e,cess deat's &0 car accidents, e,posure is t'e num&er o people
involved over a speciied period o time, and 'aJard is t'e num&er o deat's per unit o population per
unit o time. 8'is is ver0 similar ormulation as or carcinogenic risk due to e,posure to 'armul
c'emicals. Restating t'is risk e9uation wit' t'e data in t'e pro&lem statement gives,

45,000 1eat's C (-7##$
6
people:;# 0ear: ;KaJard:
*olving or KaJard we calculate,

KaJard C
45,000 1eat's
;-7##$
6
"eople:;# 0ear:
C 1.61#$
!2

1eat's
Bo. "eople L 0ear
8'e num&er o deat's e,pected in >inneapolis!*t. "aul over a t'ree!da0 weekend is

Risk C ;- 10
6
"eople:
3 da0s
36+ da0s @ 0r

_
,

1.6110
4
1eat's
Bo. "eople L 0r

_
,

C -.63 deat's

%. !ault Tree Analysis
8'e ault tree or t'e collection sump is
6
*ump
5verlows
Bo Darn!
ing Alarm
%alve ails
to 5pen
And
*ensor M#
(ails
Alarm
(ails
*ensor M-
(ails
*olenoid
(ails
5r 5r

.. To1icity Testing: Esta+lishing a Reference Dose for #uman #ealth
I an animal stud0 0ields a no o&serva&le adverse eects level ;B5AEL:, t'e ormula or determining a
'uman 'ealt' accepta&le dose is
RfD
NOAEL
F
A
F
H
w'ere F
A
is a saet0 actor o #$ or using animal studies and F
H
is anot'er saet0 actor o #$ to account or
varia&ilit0 in to,ic response in a 'uman population. I t'e animal studies were &ased on su&c'ronic e,posure,
anot'er saet0 actor o #$ would &e used in t'e denominator to e,trapolate t'e results to c'ronic e,posure in
'umans.

0. Reference Dose Calculation
(or tris;-!c'loroet'0l: p'osp'ate, B5AEL C -- mg@kg!da0 and L5AEL C 22 mg@kg!da0 or increased
weig'ts o t'e liver and kidne0s in rats.
4sing t'e B5AEL:

RfD
NOAEL
F
A
F
H
F
S
22 mg @ kg ! da0
#$ , #$ , #$
.022 mg @ kg ! da0
4sing t'e L5AEL:

RfD
LOAEL
F
A
F
H
F
S
F
L
44 mg @ kg ! da0
#$ , #$ , #$ , #$
.0044 mg @ kg ! da0
8'e lesser o t'e two values would &e c'osen or t'e R1.

2. Choice of a Safe Solvent for a Photoresist
a: Rank solvents &ased on to,icit0 rom 'ig'er to lower 'aJard
"EL ;ppm:
diet'0lemine -+
monomet'0l et'er -+
urur0l alco'ol +$
et'0lene gl0col +$
n!&ut0l acetate #+$
met'0l et'0l ketone -$$
.
et'0l acetate 2$$
&: Rank rom 'ig'er to lower e,posure potential using vapor pressure
%apor "ress. ;k"a N -+HC:
diet'0lemine 3$.#
et'0l acetate #-.6
met'0l et'0l ketone #-.#
monomet'0l et'er #.3
n!&ut0l acetate #.3
urur0l alco'ol $.#
et'0lene gl0col $.$$7
c: Considering 'aJard and e,posure, rank rom 'ig'er to lower risk
I we take t'e inverse o t'e "EL as a measure o potential 'aJard and multipl0 &0 t'e vapor pressure ;a
measure o e,posure:, we could estimate t'e overall risk potential &0 in'alation.
#@"EL L %apor "ress.
diet'0lemine #@-+ L 3$.# C #.-$
met'0l et'0l ketone #@-$$ L #-.# C $.$6
monomet'0l et'er #@-+ L #.3 C $.$+
et'0l acetate #@2$$ L #-.6 C $.$3
n!&ut0l acetate #@#+$ L #.3 C $.$$6
urur0l alco'ol #@+$ L $.# C $.$$-
et'0lene gl0col #@+$ L $.$$7 C $.$$$#6
Et'0lene gl0col is t'e solvent wit' t'e lowest risk.
d: 8o lower t'e risk even more, process modiications could &e placed on t'e integrated circuits a&rication
process to reduce t'e amount o vapor generated and to collect and recover an0 vapors prior to e,posure to
workers.

7
5. Carcinogenic Ris4 Assessment -ear a Refinery
a: In'alation dos, I
INH
:
&: In'alation Carcinogenic Risk

In'alation Carcinogenic Risk C I
INH
SF
C $.$-33#
mg )enJene
kg )DL da0

_
,

2.9 10
2
mg )enJene
kg )D L da0

1
]
1
1

_
,

C 6..6 #$
!2
c: Risk o cancer due to in'alation is greater t'an t'e recommended range o O #$
!2
to #$
!6
.
d: 8'is calculation mig't actuall0 over predict t'e risk &ecause RR and A)* were assumed to &e # w'en
actuall0 t'e0 would &e less t'an one &ut greater t'an Jero. Also, we used t'e outside concentration o
&enJene in t'e air, not t'e inside ;t'e 'ome: concentration w'ic' will &e lower. In addition, we assumed a .$
0ear e,posure duration ;E1: w'en oten people move and actuall0 spend muc' less time in an0 given 'ome.

6
Cha(ter .. Environmental 6a/ and Regulations: !rom End7of7Pi(e to Pollution
Prevention

'. Provide definitions of the follo/ing terms
a: pollution prevention: An0 act o source reduction, in!process rec0cle, on!site rec0cle, and o!site
rec0cle t'at reduces t'e amounts o releases and t'e 'aJardous c'aracteristics o t'ose releases w'ic'
ultimatel0 reac' t'e environment.
&: source reduction: An0 modiication o a manuacturing process or o production procedures w'ic'
reduces t'e amount o components entering a waste stream or t'e 'aJardous c'aracteristics o t'ose
components entering waste streams prior to rec0cle, treatment, or disposal.
c: in!process versus on!site versus o!site rec0cle: In!process rec0cle is t'e recover0 and return o
components t'at would ot'erwise &ecome waste to t'e process unit w'ere t'ese components were
generated, usuall0 immediatel0 ater t'e0 are generated. E,amples would &e unconverted reactants
leaving a reactor t'at are separated and returned to t'e reactor inlet. 5n!site rec0cle is t'e recover0 o
valua&le stream components using process units wit'in t'e same acilit0 w'ere t'ose components were
generated. 5!site rec0cle is t'e recover0 o valua&le components at a remote location rom waste
streams generated at a acilit0 and t'e return o t'e valua&le components to t'e acilit0.
d: waste treatment: An0 process t'at renders a waste stream less 'aJardous prior to disposal or direct
release t'roug' p'0sical, &iological, or c'emical means. E,amples are primar0, secondar0, and tertiar0
wastewater treatment, adsorption o volatile organic compounds rom air, and landtreatment o petroleum
'0drocar&on sludges rom tank &ottoms.
e: disposal: Long!term isolation o raw or treated waste components in a secured landill. E,amples
include landills or domestic and industrial 'aJardous and non!'aJardous waste.
: direct release: 8'e direct release o components rom processes to t'e air, land, or water. An e,ample
o t'is includes t'e release o volatile organic compounds rom ugitive emission sources in c'emical or
petroleum reiner0 processes ;rom valves, ittings, pumps, langes, connectors, etc.:.

%. Solvent Recovery and Recycle for Automo+ile Assem+ly Paint (erations
8'is rec0cle operation is an e,ample o o!site rec0cle. 8'e location o t'e solvent recover0 acilit0 is
remote rom t'e locations o automo&ile manuacture. 8'e eed or t'e solvent recover0 acilit0 is t'e
waste streams rom t'ese cleaning processes in automo&ile assem&l0 painting. 8'is activit0 would &e
considered pollution prevention using t'e e,panded deinition in t'is te,t &ut would not &e considered
pollution prevention &0 t'e ederal deinition, w'ic' onl0 includes source reduction and in!process
rec0cle.

.. Ca(ital and (erating Costs for !ederal Regulations
a) The Toxic Substances Control Act (TSCA) of 1976
C'emical manuacturers must su&mit inormation on e,isting c'emicals. 8'is inormation includes
c'emical identit0, name and molecular structure, categories o use, amounts manuactured or processed,
#$
&0products rom manuacture, processing, use, or disposal, environmental@'ealt' eects o c'emical and
&0products, and e,posure inormation. Companies must also keep records o an0 incidents involving t'e
c'emical t'at resulted in adverse 'ealt' eects or environmental damage. C'emical manuacturers,
importers, and processors are re9uired to noti0 E"A wit'in 6$ da0s o introducing a new c'emical into
commerce &0 su&mitting a "remanuacturing Botice ;">B:.
b) The Federal Insecticide, Fungicide, and Rodenticide Act (FIFRA) of 1972
8'e decision &0 E"A to register a pesticide is &ased on t'e data su&mitted &0 t'e pesticide manuacturer
in t'e registration application. 8'e data in t'e registration application is diicult and e,pensive to
develop. A registration is valid or ive 0ears, upon w'ic' time it automaticall0 e,pires unless a re!
registration petition is received. (I(RA re9uires older pesticides t'at were never su&Pect to t'e current
registration re9uirements to &e registered i t'eir use is to continue.
c: The Occupational Safety and Health Act (OSH Act) of 1970
8'e 5*K ActFs KaJard Communication *tandard re9uires t'at several standards &e met &0 manuacturers
or importers o c'emicals and also or t'e su&se9uent users o t'em. 8'ese re9uirements include t'e
development o 'aJard assessment data, t'e la&eling o c'emical su&stances, and t'e inorming and
training o emplo0ees in t'e sae use o c'emicals. 8'is inormation must &e assem&led in a material
saet0 data s'eet ;>*1*: in accordance wit' 5*K Act standards and accompan0 an0 sale or transer o
t'e c'emical. Emplo0ers must also develop a written 'aJards communication plan w'ic' outlines t'e
implementation plan or inorming and training emplo0ees on t'e sae 'andling o c'emicals in t'e
workplace. Emplo0ers must keep records o all steps taken to compl0 wit' 5*K Act re9uirements and
emplo0ers must keep records o all work!related inPuries and deat's and report t'em periodicall0 to
5*KA.
d: lean Ai! Act (AA) of 197"
"rior to t'e completion o new acilities or additions to e,isting acilities, a permit must &e o&tained rom
t'e state air 9ualit0 aut'orit0. >anuacturers must compl0 wit' t'e state!mandated source!speciic
emission limits on mo&ile and stationar0 sources at a suicient level to assure compliance wit' ederal
9ualit0 standards. >eeting t'ese re9uirements is ac'ieved &0 installing pollution control e9uipment on
waste streams leaving t'e process or &0 modi0ing t'e process to eliminate t'e waste streams.
e: The lean #ate! Act (#A) of 197$
8'e Bational "ollutant 1isc'arge Elimination *0stem ;B"1E*: permit program re9uires an0 point source
o pollution to o&tain a permit. B"1E* permits contain eluent limits, eit'er re9uiring t'e installation o
speciic pollutant treatment tec'nologies or ad'erence to speciied numerical disc'arge limits. B"1E*
permit 'olders must monitor disc'arges, collect data, and keep records o t'e pollutant levels o t'eir
eluents. 8'ese records must &e su&mitted to t'e agenc0 t'at granted t'e B"1E* permit in order to
assure t'at t'e point source is not e,ceeding t'e eluent disc'arge limits. A permit must &e o&tained rom
t'e 4nited *tates Arm0 Corp o Engineers &eore an0 disc'arge o dredge or ill materials occurs into
naviga&le waterwa0s, including wetlands.
: Re%ou!ce on%e!&ation and Reco&e!y Act (RRA) of 197'
A generator o 'aJardous waste must o&tain an E"A identiication num&er wit'in 6$ da0s o t'e initial
generation o t'e waste. RCRA re9uires generators to properl0 package 'aJardous waste or s'ipment
o!site and to use approved la&eling and s'ipping containers. /enerators must maintain records o t'e
##
9uantit0 o 'aJardous waste generated, w'ere t'e waste was sent to or treatment, storage, or disposal, and
ile t'is data in &iennial reports to t'e E"A. /enerators must prepare a 4niorm KaJardous Daste
>aniest, w'ic' is a s'ipping document t'at must accompan0 t'e waste at all times. A cop0 o t'e
maniest will &e sent &ack to t'e generator &0 t'e treatment acilit0 to assure t'at t'e waste reac'ed its
proper destination.
g: The o(p!ehen%i&e En&i!on(ental Re%pon%e) o(pen%ation) and *ia+ility Act (ER*A) of 19,"
Ater a site is listed in t'e Bational "riorit0 List, E"A identiies potentiall0 responsi&le parties ;"R"s: and
notiies t'em o t'eir potential CERCLA lia&ilit0. I a clean up is conducted &0 t'e E"A, t'e "R"s are
responsi&le or pa0ing t'eir s'are o t'e clean up costs. I t'e clean up 'as not &egun, "R"s can &e
ordered to complete t'e clean up o t'e site.
': The E(e!-ency .lannin- and o((unity Ri-ht to /no0 Act (E.RA
E"CRA re9uires acilities wit' more t'an #$ emplo0ees w'o eit'er use more t'an #$,$$$ pounds or
manuacture or process more t'an -+,$$$ pounds o one o t'e listed c'emicals or categories o c'emicals
to report annuall0 to E"A. 8'e report must contain data on t'e ma,imum amount o t'e to,ic su&stance
on!site in t'e previous 0ear, t'e treatment and disposal met'ods used, and t'e amounts released to t'e
environment or transerred o!site or treatment and@or disposal.
i: .ollution .!e&ention Act of 199"
8'e onl0 mandator0 provisions o t'e ""A re9uires owners and operators o acilities t'at are re9uired to
ile a orm R under t'e *ARA 8itle III ;t'e 8RI: to report to t'e E"A inormation regarding t'e source
reduction and rec0cling eorts t'at t'e acilit0 'as undertaken during t'e previous 0ear.

0. Source Reduction Categories
a: *pecialt0 Aromatic Compound ;*AC:: 5n!line instrumentation or pK control on t'e raw materials
process is an e,ample o e1uip(ent o! technolo-y (odification. Lowering reactor temperature in t'e
*AC process is an e,ample o p!oce%% o! p!ocedu!e (odification%.
&: *pecialt0 Alco'ol ;*A: process: Improved reaction step t'at reduced impurit0 levels and eliminated t'e
was' step waste is an e,ample o p!oce%% o! p!ocedu!e (odification%.

#-
Cha(ter 0. Roles and Res(onsi+ilities of Chemical Engineers

'. Com(are )nherently Safer Design /ith Pollution Prevention
)nherently Safer Design Conce(ts Pollution Prevention Conce(ts
)ntent: reduce catastrop'ic releases o
'aJardous c'emicals and t'e 'aJards o t'ose
releases &0 modi0ing t'e process to eliminate
t'e source o t'ose 'aJards wit'in t'e process.
)ntent: reduce c'ronic releases o 'aJardous
c'emicals and t'e 'aJards o t'ose releases &0
modi0ing t'e process to make t'em more
eicient at using energ0 and mass.
Minimi3e: reduce t'e inventor0 o 'aJardous
c'emicals wit'in t'e process.
*ource Reduction: reduce t'e generation and
release o 'aJardous wastes rom a process.
*u&stitute: replace 'aJardous materials wit'
saer c'emicals to reduce impacts o
catastrop'ic releases.
>aterial *u&stitution: replace 'aJardous
materials or materials t'at use e,cessive energ0
wit' more &enign materials.
>oderate: 4se less 'aJardous conditions to
lessen t'e impacts o an0 catastrop'ic releases.
"rocess@"rocedure >odiications: c'ange
process conditions to reduce waste generation
and energ0 consumption.
*impli0: design acilities to &e less comple,
and less error prone, and orgiving o an0
errors t'at are made.
"rocess >odiication: c'ange t'e process
control strateg0 to more precisel0 ac'ieve t'e
desired operating conditions.

%. Effects of Chemical Pro(erties
*aet0 Concerns: C'emical properties t'at would indicate t'e potential or catastrop'ic release would &e
&oiling point, reactivit0 wit' air or water, vapor pressure, corrosivit0 to process vessels, endot'ermic or
e,ot'ermic 'eat o reaction, ..
"ollution "revention Concerns: C'emical properties t'at would reduce t'e potential or c'ronic release
rom process operations include &oiling point, vapor pressure, solu&ilit0 in water, emulsion orming wit'
water, Kenr0Is constant, compati&ilit0 wit' process materials suc' as gaskets and valve stems, corrosivit0
to process vessels, Q

.. -e/ 8-atural8 Product from ,otanicals: Ethanol vs. n7#e1ane
"'0sical@8o,icological "roperties ;reerence needed:
"roperties Et'anol n!Ke,ane
8o,icit0 ;L1+$, oral rat, mg@kg: .$6$ R+$$$
8o,icit0 ;5*KA "EL, ppm: #$$$ +$
#3
Carcinogenic no no
)oiling "oint ;HC N # atm: .7.3 67..
>elting "oint ;HC: !##2 !6+
%apor "ressure ;mm Kg N -$HC: 22.6 #-6
%apor 1ensit0 ;air C #.$: #.+6 3
Li9uid 1ensit0 ;speciic gravit0: $..76 $.6+6
*olu&ilit0 in Dater Ininite Begligi&le
(las' "oint ;HC: 7.6 !-3
Lower E,plosive Limit ;A: 3.3 #.-
4pper E,plosive Limit ;A: -2.+ ...
Reactivit0 *ta&le *ta&le
(ederal Environmental "ermits@Reporting ;reerence needed:
Environmental Regulation Et'anol n!Ke,ane
8*CA ">B application 0es 0es
5*K Re9uirements 0es 0es
(I(RA no no
CAA permit 0es 0es
CDA permit 0es 0es
RCRA Reporting no no
E"CRA Reporting no 0es
CERCLA Reporting no 0es
""A Reporting no 0es
a: I t'e decision is &ased on a comparison &etween t'e solvents, t'en et'anol would &e c'osen or t'e
process. Et'anol 'as a lower to,icit0 Pudging rom t'e >*1* inormation and 'as ewer reporting
re9uirements compared to n!'e,ane. 5 course, more inormation would &e needed to make a reasona&le
decision. De must know w'at eects t'e solvent c'oice will 'ave on operating costs, on energ0
consumption, and 9ualit0 o product. In addition, we must know w'at eects o solvent c'oice will 'ave
on overall environmental impact o t'e process, including energ0!related emissions and impacts, w'ic'
can &e signiicant relative to t'e impacts o t'e process materials. >et'ods or evaluating environmental
impacts during process design are t'e topics o discussion or "art II o t'e &ook.
&: A C'emical EngineerFs responsi&ilities are to 'im or 'er sel, to t'e emplo0er, t'e communit0, and t'e
customer. Eac' o t'ese responsi&ilities must &e incorporated into an0 decision regarding product and
process design. A potential plant closure resulting in loss o Po&s s'ould not inluence t'e decision as to
w'et'er a product will &e produced or 'ow it will &e produced. 8'e primar0 decision varia&les are
w'et'er t'e process and product are proita&le, w'ic' means t'at societ0 values it, and w'et'er t'e
process and product causes unaccepta&le damage to t'e environment and 'uman 'ealt'.
c: *ame as &:.

#2
Cha(ter 2. Evaluating Environmental !ate: A((roaches ,ased on Chemical
Structure

'. Estimate (ro(erties for nitro+en3ene.
Bitro&enJene 'as t'e molecular ormula
)oiling "t., rom e9n. +!#,
8
&
;E: C #67.- G n
i
g
i
group g
i
contri&ution
B5
-
##3.66
# aaC 3$..6 ;a su&stituted car&on &ound to - aromatic car&ons:
+ aaCK +;-7.+3:
8
&
;E: C #67.- G ##3.66 G 3$..6 G +;-7.+3: C 27+.6$ E estimated
C 272.#- E actual
8
&
;corrected: C 8
&
= 62.72 G $.++..8
&
= $.$$$..$+;8
&
:
-
S8
&
.$$ET ;E9n. +!-:
C 27+.6 = 62.72 G $.++..;27+.6: = $.$$$..$+;27+.6:
-
C 2.6.6 E
8
&
;corrected: is in error &0 $.7.A compared to t'e actual value.
%apor pressure ;"
vp
::
ln "
vp
C SA;8
&
= C:
-
T U S#@;8
&
= C: ! #@;8 = C:T ;E9n. +!.:
S$.6. R 8
&
T
A C E
(
;7..+ G R ln 8
&
: C #.$+;7..+ G #.67. ln;27+.6:: C --.$6
C C !#7 G $.#6 8
&
C !#7 G $.#6;27+.6: C .2.-6
ln "
vp
C S--.$6;27+.6 = .2.-6:
-
T U S#@;27+.6 = .2.-6: ! #@;-67 = .2.-6:T C !7.#36
S$.6. ;#.67.: ;27+.6: T
"
vp
C e,p;!7.#3: C -.6-,#$
!2
atm C $.-- mm Kg.
Kenr0Fs Law constant ;K:
!log K C log ;air!water partition coeicient: C n
i
'
i
G n
P
c
P
;K unitless:
# C
aromatic
!B5
-
n
i
'
i
C -.266
6 C
aromatic
! C
aromatic
n
i
'
i
C 6;$.-637:
+ C
aromatic
!K n
i
'
i
C +;!$.#+23:
Bo corrections actors
!log K C -.-266 G 6;$. -637: G +;!$.#+23: C 3.$6
K C #$
!3.$6
C 7.66,#$
!2
unitless C -.#3,#$
!2
atm!m
3
@mole
K ;e,perimental: C -.2$,#$
!2
atm!m
3
@mole
#+
B5
-
5ctanol!water partition coeicient ;E
ow
::
log E
ow
C $.--6 G n
i

i
G n
P
c
P
6 C
aromatic
n
i
'
i
C 6;$.-62$:
!B5
-
;aromatic attac'.: n
i
'
i
C !$.#7-3
Bo corrections actors
log E
ow
C $.--6 G 6;$.-62$: G !$.#7-3 C #.7#
E
ow
C #$
#.7#
C 62.6.
log E
ow
;e,perimental: C #.7+
Dater solu&ilit0 ;*:: ;* in mole@L:
log * C $..66 = $.7+2 log E
ow
! $.$$.-7;>D: G '
P
;used w'en melting pt. not availa&le:
Corrections actors '
P
C !.36$ ;aromatic nitro group:
log * C $..66 = $.7+2;#.7+: ! $.$$.-7;#-3.##: G !.36$ C !-.$.
* C #$
!-.$.
C7.+#,#$
!3
moles@L C #.$+ g@L C #,$2..+ mg@L
*oil sorption coeicient ;E
oc
::
log E
oc
C $.+3
#
G $.6- G n
P
"
P
;E
oc
is ratio o g@g car&on to g@ml solution:
#
C ;
i
U
P
:
!$.+
, t'e irst order molecular connectivit0 inde,
i
,t'e connectedness o car&on or ot'er 'eteroatom i:
)ond connectedness ;
i
U
P
:
;B!5: ;BC5: ;B!C: -;C!C: 2;C!C:
;3,#: ;3,#: ;3,3: -;3,-: 2;-,-:
#
C ;
i
U
P
:
!$.+

#
C
1
3
+
1
3
+
1
9
+ 2
1
6
+ 4
1
4
C 2.3$+
log E
oc
C $.+3;2.3$+: G $.6- ! $.63- C -.-.
E
oc
C #$
-.-.
C #76
Atmosp'eric 'al lie:
8'e onl0 signiicant reaction is addition to aromatic ring C $.-23.,#$
!#-
cm
3
@molecule!sec.
t
#@-V
C ln ;-: @ ;k S5K
.
T: C $.663@;;$.-23.,#$
!#-
cm
3
@molecule!sec:;#.+,#$
6
molecules@ cm
3
::
t
#@-V
C #.766,#$
6
sec C -- da0s.
)iodegrada&ilit0:
I C 3.#66 G a
#
#
G a
-
-
GQQ G a
n
n
G a
m
>D
4nsu&stituted p'en0l group a

C $.$--
Aromatic ;B5
-
: a

C !.#32 ;used aromatic amine as su&stitute:
>olecular weig't a

C !$.$$--#
I C 3.#66 G $.$-- ! .#32 G #-3.##;!$.$$--#: C -.7# ;weeks to a mont':

%. Estimate (ro(erties for %7Chloroaniline
#6
B
5 5
# #
3
3
-
-
-
-
-
(rom t'e E"IDIB sotware, enter t'e CA* Bum&er o 6+!+#!-. 8'e ollowing summar0 is o&tained wit'
t'e sotware output listed directl0 &elow.
)oiling point ;8
&
: -#6.$+ HC
%apor pressure ;"
vp
: at 3$$ E $.#6 mm Kg N -+HC
Kenr0Fs Law constant ;K: #.2#,#$
!6
atm!m
3
@mole using &ond met'od
5ctanol!water partition coeicient ;E
ow
: Log E
ow
C #..-
)ioconcentration (actor ;)C(: Log )C( C $..63 using )C(win
Dater solu&ilit0 ;*: --2# mg@L ! no melting pt. ormula used.
*oil sorption coeicient ;E
oc
: Log E
oc
C #.766
Atmosp'eric 'al lie $.32$ 1a0s ;#-!'r da0W #.+E6 5K@cm
3
:
)iodegrada&ilit0 -.+.+. ;weeks!mont's:
SMILES : Nc(c(ccc1)CL)c1
CHEM : Benzenamine, 2-chloro-
CAS NUM: 0000!-!1-2
M"L #"$: C% H% CL1 N1
M"L &' : 12()!(
------------------------------ E*I SUMMA$+ (,2)-0) --------------------------
*h./ical *ro0er1. In021/:
&a1er Sol23ili1. (m45L): ------
6a0or *re//2re (mm H4) : ------
Henr. LC (a1m-m75mole) : ------
Lo4 8o9 (oc1anol-9a1er): ------
Boilin4 *oin1 (:e4 C) : ------
Mel1in4 *oin1 (:e4 C) : ------
Lo4 "c1anol-&a1er *ar1i1ion Coe; (S$C):
Lo4 8o9 (8"&&IN ,1)%0 e/1ima1e) < 1)(2
Lo4 8o9 (E=0er) :a1a3a/e ma1ch) < 1)0
Boilin4 *1, Mel1in4 *1, 6a0or *re//2re E/1ima1ion/ (M*B*&IN ,1)2>):
Boilin4 *1 (:e4 C): 21%)0! (A:a01e: S1ein ? Bro9n me1ho:)
Mel1in4 *1 (:e4 C): 2-)-1 (Mean or &ei4h1e: M*)
6*(mm H4,2! :e4 C): 0)1% (Mean 6* o; An1oine ? @rain me1ho:/)
&a1er Sol23ili1. E/1ima1e ;rom Lo4 8o9 (&S8"& ,1)70):
&a1er Sol23ili1. a1 2! :e4 C (m45L): 22-1
lo4 8o9 2/e:: 1)0 (e=0Ao9 :a1a3a/e)
no-mel1in4 01 eB2a1ion 2/e:
EC"SA$ Cla// *ro4ram (EC"SA$ ,0)3):
Cla//(e/) ;o2n::
Aroma1ic Amine/
Henr./ La9 Con/1an1 (2! :e4 C) CHEN$+&IN ,7)00D:
Bon: Me1ho: : 1)-1E-00% a1m-m75mole
@ro20 Me1ho:: 1)>%E-00% a1m-m75mole
*ro3a3ili1. o; $a0i: Bio:e4ra:a1ion (BI"&IN ,7)%7):
Linear Mo:el : 0)2(0%
#.
Non-Linear Mo:el : 0)0%1!
E=0er1 S2r,e. Bio:e4ra:a1ion $e/2l1/:
Ul1ima1e S2r,e. Mo:el: 2)!(!( (9eeA/-mon1h/)
*rimar. S2r,e. Mo:el : 7)700 (:a./-9eeA/ )
A1mo/0heric "=i:a1ion (2! :e4 C) CAo0&in ,1)>(D:
H.:ro=.l $a:ical/ $eac1ion:
"6E$ALL "H $a1e Con/1an1 < 71)-2( E-12 cm75molec2le-/ec
Hal;-Li;e < 0)7-0 Ea./ (12-hr :a.F 1)!E% "H5cm7)
Hal;-Li;e < -)0>- Hr/
"zone $eac1ion:
No "zone $eac1ion E/1ima1ion
Soil A:/or01ion Coe;;icien1 (*C8"C&IN ,1)%7):
8oc : (-)0-
Lo4 8oc: 1)>%
AB2eo2/ Ba/e5Aci:-Ca1al.ze: H.:rol./i/ (2! :e4 C) CH+E$"&IN ,1)%-D:
$a1e con/1an1/ can N"' 3e e/1ima1e: ;or 1hi/ /1r2c12reG
BC# E/1ima1e ;rom Lo4 8o9 (BC#&IN ,2)10):
Lo4 BC# < 0)(%7 (BC# < !)(-)
lo4 8o9 2/e:: 1)0 (e=0Ao9 :a1a3a/e)
6ola1iliza1ion ;rom &a1er:
Henr. LC: 1)>%E-00% a1m-m75mole (e/1ima1e: 3. @ro20 SA$ Me1ho:)
Hal;-Li;e ;rom Mo:el $i,er: !7%)% ho2r/ (22)7% :a./)
Hal;-Li;e ;rom Mo:el LaAe : 7>% ho2r/ (1%%)1 :a./)
$emo,al In &a/1e9a1er 'rea1men1:
'o1al remo,al: 2)2( 0ercen1
'o1al 3io:e4ra:a1ion: 0)0 0ercen1
'o1al /l2:4e a:/or01ion: 2)0( 0ercen1
'o1al 1o Air: 0)11 0ercen1
!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!

.. Estimate (ro(erties. EP)/in results are sho/n +elo/.
.!ope!ty Ethanol 12p!opanol 12hexanol n2p!opane n2hexane
)oiling point ;8
&
:
;HC:
6+.## 76.66 #+6.$6 !...6 .#.+3
%apor pressure ;"
vp
:
;mm Kg N -+HC:
##6 33.6 $.7$6 -.-6,#$
3
#3+
Kenr0Fs Law constant
;K:
+.6.,#$
!+
..+-,#$
!6
#..6,#$
!+
..3,#$
!#
#..#
#7
;atm!m
3
@mole:
5ctanol!water partition
coeicient, Log ;E
ow
:
!$.#2 $.3+ #.7- #.7# 3.-6
Dater solu&ilit0 ;*:
;mg@L:
..6-,#$
+
-..-,#$
+
6,77+ 366 #..-2
*oil sorption
coeicient Log ;E
oc
:
$.$$ $.#-- $.6-$ #.36. -.#.
Atmosp'eric 'al lie
;da0s:
-.66 #.6+ #.#$ 7.23 #.66
)iodegrada&ilit0
;"rimar0 *urve0
>odel:
3.6#
;da0s:
3.76
;da0s:
2.#$
;da0s:
3..7
;da0s:
3.66
;da0s:
(or eac' o t'e properties, comment on w'et'er molecular weig't or t'e presence o a '0drogen &onding
group 'as a more pronounced eect on c'emical properties.
)oiling point ;8
&
: '0drogen &onding
%apor pressure ;"
vp
: '0drogen &onding
Kenr0Fs Law constant '0drogen &onding
5ctanol!water partition coeicient &ot'
Dater solu&ilit0 ;*: '0drogen &onding
*oil sorption coeicient '0drogen &onding
Atmosp'eric 'al lie molecular weig't
)iodegrada&ilit0 neit'er

0. ,en3ene discharge to a river.
8otal disc'arge rate to "58D C -,$$$ kg &enJene @ da0
Removal eicienc0 in "58D C 7+A
Bet &enJene disc'arge to river C ;#!.7+: -,$$$ kg &enJene@da0 C 3$$ kg &enJene@da0
a: Estimate raction o &enJene in water, sediment, and &iota at disc'arge point.
(rom E"Iwin, CA* no. .#!23!-
Log Eoc C -.-#6, Eoc C #6+.+ L water@kg or kg water@kg sediment car&on
Log )C( C $.62$, )C( C 7..#- L water@kg or kg water@kg &iota
)ased on t'e river low rate t'e total low rates o water, sediment and &iota are:
Dater: ;#,-+$ ,#$
6
liter@da0 U # kg@liter: C #,-+$ ,#$
6
kg@da0
#6
*ediment: #,-+$ ,#$
6
kg@da0 U #+ kg sediment car&on@ #$
6
kg water C #7,.+$ kg sediment C@da0
)iota: #,-+$ ,#$
6
kg@da0 U $.# kg &iota@ $.# ,#$
6
kg water C #,-+$ kg &iota@da0
>ass &alance: <rate o &enJene disc'arge to river? C <rate o &enJene low downriver in water, sediment,
and &iota?.
3$$ &enJene kg@da0 C #,-+$,#$
6
kg water@da0 ;C
water
: G #7,.+$ kg sediment car&on@da0 ;#6+.+ kg
water@kg sediment car&on: C
water
G #,-+$ kg &iota@da0 ;7..#- kg water@kg &iota: C
water
C
water
C -.36,#$
!.
kg &enJene@kg water C .-36 ppm &enJene in water.
(raction &enJene in water C #,-+$,#$
6
kg water@da0 ;C
water
: @ 3$$ kg &enJene@da0 C 66..+A
(raction &enJene in sediment
C #7,.+$ kg sediment car&on@da0 ;#6+.+ kg water@kg sediment car&on: C
water
@3$$ C .-2.A
(raction &enJene in &iota C #,-+$ kg &iota@da0 ;7..#- kg water@kg &iota: C
water
@ 3$$ C .$$$6A
&: Is volatiliJation o &enJene rom t'e river importantX
Assume air a&ove river to #$ m 'eig't is in e9uili&rium wit' &enJene in water at disc'arge point
concentration or t'e ull #$$ km lengt' o t'e river.
4se Kenr0Fs constant to estimate t'e air concentration
(rom E"Iwin, K C +.36,#$
!3
atm!m
3
@mole
Air Concentration C K C
water
w'en e,pressed in units o moles &enJene @ m
3
C ;+.36,#$
!3
atm!m
3
@mole:;-.36,#$
!.
kg &enJene@kg water:;# mole@.$.7## kg
&enJene:;#$$$ kg water @ m
3
: C #.6+,#$
!+
atm
C #.6+,#$
!+
atm ;# mole &enJene@mole airLatm:;.$.7## kg &enJene@mole &J:
;# mole air@.$--2 m
3
air: C +..+,#$
!+
kg &enJene @ m
3
air
8otal )enJene in air C ;+..+,#$
!+
kg @m
3
air:;#$ m:;3$ m:;23.- km:;#$$$ m@km: C .2+ kg &enJ
Bote = 23.- km is t'e distance t'at t'e river lows in # da0.
)ecause t'is estimate is muc' greater t'an t'e input o &enJene into t'e river, volatiliJation is important.
c: Estimate t'e raction t'at &iodegrades prior to reac'ing t'e water inlet #$$ km downriver.
8ime to reac' #$$ km downriver is ;#$$ km:@;23.- km@da0: C -.3 da0s
(rom E"Iwin, &iodegradation takes weeks = mont's, so raction &iodegraded is insigniicant.
d: Estimate t'e potential to,icit0 o t'e releases to a9uatic lie
(rom E"Iwin, Log Eow C #.66, >D C .7.##
A correlation or to,icit0 to guppies or c'loro&enJenes is given &0
log ;#@LC
+$
: C $.7.# log E
ow
! 2.7., w'ere LC
+$
is e,pressed in units o mol@L.
log ;#@LC
+$
: C $.7.# ;#.66: ! 2.7. C !3.#2
#@LC
+$
C #$
!3.#2
C ..3$,#$
!2
LC
+$
C #,3.$ mol@L
C
water
C -.36,#$
!.
kg &enJene@kg water rom part a: C -.36,#$
!2
g &enJene@L water
C 3.$6 mol@L, t'us t'is concentration is not likel0 to pose a risk to is' since it is muc' less t'an
t'e LC
+$
.

-$
2. Estimate the amount of he1achloro+en3ene 9#1: that /ould +e ingested if a (erson /ere to eat a
&.2 4g fish from the (ond.
# kg 'e,ac'loro&enJene added to a pond
"ond water content C #$
+
m
3
or #$
7
kg water
5rganic car&on sediment content C #$ kg organic car&on sediment @ #$
6
kg water C #$
!+
kg@kg
(is' content C #$$ g is' @ #$$ m
3
or $.# kg is' @ #$
+
kg water
(rom E"Iwin, wit' CA* no. o ##7!.2!#
Eoc C 3,377 L water@kg org. C
)C( C +,#+- L water @ kg is'
>ass &alance: # kg K, C >
w
G >
s
G >
w'ere
>
w
is t'e mass in water C ;#$
7
kg water:C
water
,
>
s
is t'e mass in sediment car&on C ;#$
!+
kg org. C@kg water:; 3,377 kg water@kg org. C: C
water
,
>
is t'e mass in is' C ;$.# kg is'@#$

+
kg water:; +,#+- kg water@kg is': C
water
.
*olving or C
water
C #,#$
!7
kg K,@kg water.
Concentration in is' C )C( , C
water

C ;+,#+- kg water @ kg is':; #,#$
!7
kg K,@kg water:
C +.#+,#$
!+
kg K,@kg is'.
Ingestion dose to 'umans C ;$.+ kg is' consumed:;+.#+,#$
!+
kg K,@kg is': C -.+7,#$
!+
kg K,

5. The Great 6a4es ,asin (artitioning of tetrachloroethylene 9PERC:
8otal emissions to t'e &asin are to air ;#.7,#$
.
pounds per 0ear:, land ;-.6,#$
6
pounds per 0ear: and water
;7.2,#$
-
pounds per 0ear: C -.$6,#$
.
pounds @ 0r C 6.32,#$
6
kg@0r
Landscape properties
.!ope!ty ai! 0ate! %oil %edi(ent
%olume ;m
3
: ..6U#$
#2
-.3U#$
#3
-.6U#$
#$
2.7U#$
7
Area ;m
-
: ..6U#$
##
-.2U#$
##
+.-U#$
##
-.2U#$
##
5rganic raction $.$- $.$2
1ensit0 ;kg@m
3
: #.- #$$$ #+$$ #-7$
Residence time ;'r: #3$ -.-,$$$ ++$ #.$$
a: Calculate t'e e9uili&rium partitioning o tetrac'loroet'0lene in t'e air, water, soil and sediment o t'e
/reat Lakes )asin .
E"Iwin provides K and Eoc, CA* no. #-.!#7!2
K ;atmLm
3
@mole: C #.6+,#$
!-

Eoc ;L ;or kg: water@kg org. C: C #$6.7
>ass &alance: Assume t'at "ERC is onl0 signiicant in organic car&on in soil and sediment
>
"ERC
C 6.32,#$
6
kg C >
air
G >
water
G >
soil
G >
sediments
>
air
;kg: C mass o "ERC in air C %
air
C
air

C %
air
"
air
;# mole "ERC@mole airLatm:;.#6+73 kg
"ERC@mole "ERC:;# mole air@.$--2 m
3
air:
C %
air
K ;C
water
:;# mole "ERC@mole airLatm: ;.#6+73 kg "ERC@mole "ERC:
;# mole air@.$--2 m
3
air:
C ;..6,#$
#2
m
3
air:;#.6+,#$
!-
atmLm
3
water@mole:;# mole "ERC@mole airLatm:
-#
;.#6+73 kg "ERC@mole "ERC:;# mole air@.$--2 m
3
air: C
water

C 6.37,#$
#3
m
3
water C
water
>
water
;kg: C mass o "ERC in water C %
water
C
water
w'ere C
water
'as units o kg "ERC@m
3
water
>
soil
;kg: C mass o "ERC in soil C %
soil
1ensit0
soil
C
soil
w'ere C
soil
is kg "ERC@kg soil
C %
soil
1ensit0
soil
;(ract. 5rg. C:
soil
Eoc ;#$
!3
m
3
water @ kg water: C
water
C ;-.6,#$
#$
m
3
:;#+$$ kg soil@ m
3
:;.$- kg org.C@kg soil:;#$6.7 kg water@kg org. C:
;#$
!3
m
3
water @ kg water: C
water
C 7.33,#$
#$
m
3
water C
water

>
sediment
;kg: C mass o "ERC in sediment C %
sed
1ensit0
sed
C
sed
w'ere C
sed
is kg "ERC@kg sed
C %
sed
1ensit0
sed
;(ract. 5rg. C:
sed
Eoc ;#$
3
kg water @ m
3
water: C
water
C ;2.7,#$
7
m
3
:;#-7$ kg sed.@m
3
:;.$2 kg org.C@kg sed.:;#$6.7 kg water@kg org. C:
;#$
!3
m
3
water @ kg water: C
water
C -.6-,#$
6
m
3
water C
water

C
water
C 6.32,#$
6
kg@;6.37,#$
#3
G-.3,#$
#3
G7.33,#$
#$
G-.6-,#$
6
: m
3
C ..66,#$
!7
kg@m
3
water
(raction in air C >
air
@6.32,#$
6
kg C ;6.37,#$
#3
m
3
water: C
water
@6.32,#$
6
kg C $.7$-
(raction in water C >
water
@6.32,#$
6
kg C %
water
C
water
@6.32,#$
6
kg C $.#6.
(raction in *oil C >
soil
@6.32,#$
6
kg C 7.33,#$
#$
m
3
water C
water
C ..#3,#$
!2
(raction in *ediment C >
sediment
@6.32,#$
6
kg C -.6-,#$
6
m
3
water C
water
C -.-2,#$
!+
&: 8'e s0stem modeled in part a: will never reac' stead0!state. "ERC will continue to accumulate
&ecause t'e model environment is a closed s0stem and t'ere are no reaction or ot'er loss mec'anism
included.
c: *tead0!state concentration in eac' environmental compartment wit' reaction
(rom E"Iwin
Atmosp'ere: 'al!lie ;t
#@-
: is +$ da0s ;or .#3. 0r: due to '0dro,0l radical o,idation. 8'e #
st
order reaction
rate constant is, k
air
C ln-@t
#@-
C ln-@;.#3. 0r: Y + 0r
!#
.
)iodegradation: 'al!lie ;: is a&out -!2 weeks ;$.# 0r: due to &iodegradation. k
water
C ln-@t
#@-
C ln-@;.# 0r: Y
. 0r
!#
.
Assume t'at &iodegradation onl0 takes place in t'e water p'ase o t'e soil and sediment and in t'e water
compartment and t'e volume o water in t'e soil and t'e sediment is appro,imatel0 t'e same as t'e soil
and sediment volumes respectivel0, in t'e a&sence o ot'er inormation.
>ass &alance: at stead0!state
Accumulation rate C $ C input rate ! ;reaction loss rates:
$ C 6.32,#$
6
kg ! %
air
k
air
C
air
! %
water
k
&io
C
water
! %
soil
k
&io
C
water
! %
sed
k
&io
C
water
$ C 6.32,#$
6
kg@0r ! 6.37,#$
#3
m
3
water k
air
C
water
! %
water
k
&io
C
water
! %
soil
k
&io
C
water
!
%
sed
k
&io
C
water
C
water
C 6.32,#$
6
kg@0r @ ;6.37,#$
#3
k
air
G k
&io
;-.3,#$
#3
G-.6,#$
#$
G2.7U#$
7
: m
3
water:
C #.27,#$
!7
kg "ERC@ m
3
water
Concentrations in eac' environmental compartment
Air: C
air
C K ;C
water
:;# mole "ERC@mole airLatm: ;.#6+73 kg "ERC@mole "ERC:
;# mole air@.$--2 m
3
air:
C ;#.6+,#$
!-
atmLm
3
water@mole:; #.27,#$
!7
kg "ERC@ m
3
water:
;# mole "ERC@mole airLatm: ;.#6+73 kg "ERC@mole "ERC:;# mole air@.$--2 m
3
air:
C #.7#,#$
!6
kg "ERC@ m
3
air
Dater: C
water
C #.27,#$
!7
kg "ERC@ m
3
water
--
*oil: C
soil
C ;(ract. 5rg. C:
soil
Eoc ;#$
!3
m
3
water @ kg water: C
water
C ;.$- kg org.C@kg soil:;#$6.7 kg water@kg org. C:;#$
!3
m
3
water @ kg water: C
water

C 3.#6,#$
!##
kg "ERC@kg soil
*ediment: C
sed
C ;(ract. 5rg. C:
sed
Eoc ;#$
!3
m
3
water @ kg water: C
water
C ;.$2 kg org.C@kg soil:;#$6.7 kg water@kg org. C:;#$
!3
m
3
water @ kg water: C
water
C 6.3-,#$
!##
kg "ERC@kg sediment
d: Eects o advection &0 wind and water low on concentrations
Advection is an additional mass loss mec'anism rom our environmental model region. Advection loss is
represented &0 t'e term /
i
C
i
w'ere / is t'e volumetric low rate o air or water ;m3@0r:, C is t'e mass
concentration o "ERC in t'e air or water, and t'e su&script i is eit'er water or air. 8'ese terms would &e
included in t'e reaction loss term in t'e stead0!state mass &alance e9uation a&ove. 8'e value o / or air
and water can &e o&tained rom t'e residence time values in t'e data ta&le &0 dividing t'e compartment
volume &0 t'e residence time. 8'us or air, /
air
C ..6,#$
#2
m
3
air @ #3$ 'rL#0r@7.6$'r C +.#-,#$
#6
m
3

air@0r. *imilarl0 or water, /
water
C -.3,#$
#3
m
3
water @ -.-,$$$ 'rL#0r@7.6$'r C ..2,#$
##
m
3
water@0r.

;. Design a solvent molecule that has a va(or (ressure greater than ' mm #g$ a molecular /eight
+et/een ;2 and '2&$ and /ill +iodegrade in less than one month.
%apor pressure: depends on &oiling point, assume 3$$E as t'e c'osen temperature
ln "
vp
;atm: C SA;8
&
= C:
-
T U S#@;8
&
= C: ! #@;8 = C:T
S$.6. R 8
&
T
CC !#7 G $.#6 8
&
A C E
(
;7..+ G R ln 8
&
:
(rom (igure "+..!#&elow, we see t'at t'e '0drocar&on must 'ave a 8
&
less t'an a&out 26$ E and greater
t'an 3$$ E, our lower limit constraint.
-3
(igure "+..!#
)oiling "oint, 8
&
;E: C #67.- G n
i
g
i
uncorrected value is ade9uate or design
(or alip'atic '0drocar&ons, gi or a !CK
3
group is -#.67 and or a RCK
-
group it is -2.--.
(igure "+..!- &elow s'ows 8
&
versus num&er o car&ons over t'e range allowed ;.+O>DO#+$:. 8'us,
t'e alip'atic '0drocar&on must &e &etween 6 and #$ car&ons to meet >D and "vp constraints.
(igure "+..!-
-2
Aliphatic Hydrocarbons
0
1
2
3
4
5
6
7
8
9
10
400 410 420 430 440 450 460 470 480
Boiling Pt. T
b
(K)
P
vp
(mm Hg)
Boiling Pt. versus Carbon Number
300
320
340
360
380
400
420
440
460
5 6 7 8 9 10
Number of Carbons
T
b
(K)
)iodegrada&ilit0 must &e greater t'an 3 according to t'e e9uation
I C 3.#66 G a
#
#
G a
-
-
GQQ G a
n
n
G a
m
>D
(or alip'atic '0drocar&ons, t'e onl0 parameter t'at is relevant is t'e molecular wt. parameter, a
m
C
!$.$$--#. (igure "+..!3 &elow s'ows t'e &iodegrada&ilit0 inde, as a unction o car&on num&er or
alip'atic '0drocar&ons
(igure "+..!3
8'e onl0 solvent candidate to satis0 all o t'e constraints is t'e 6!car&on '0drocar&on, n!'e,ane. 5t'er
classes o organic compounds could 'ave &een c'osen or t'is design.

<. Design a solvent molecule that has a va(or (ressure less than ' mm #g 9at .&& ":$ a molecular
/eight +et/een ;2 and '2&$ and /ill +iodegrade in less than one month.
Rat'er t'an taking a s0stematic approac' similar to pro&lem ., we will instead appl0 our knowledge o
t'e eects o unctional groups on &oiling point, vapor pressure, molecular weig't, and &iodegrada&ilit0.
8'e &oiling point must &e greater t'an 26$ in order to meet t'e vapor pressure constraint, as s'own in
(igure "+..!#. 5ne o t'e unctional groups in 8a&le +.-!- t'at 'as a large eect on &oiling point is t'e
'0dro,0l group. Adding t'is unctional group to an alip'atic '0drocar&on will dramaticall0 increase
&oiling point and decrease vapor pressure. 8'is same unctional group also en'ances &iodegrada&ilit0, as
s'own &0 t'e positive contri&ution in 8a&le +.3!2. Adding t'e '0dro,0l unctional group ac'ieves &ot'
goals simultaneousl0. 8'ereore, we estimate t'e properties or #,2!&utanediol, K5!CK
-
!CK
-
!CK
-
!CK
-
!
5K.
-+
Biodegradability Index
2.86
2.88
2.9
2.92
2.94
2.96
2.98
3
3.02
0 2 4 6 8 10 12
Number of Carbons
I
n
e
d
x
4sing E"Iwin
CA* Bo. ##$!63!2
8'e molecular weig't is 6$.#-, wit'in t'e re9uired range
)oiling "t. C #6+.6 C C 267..+ E
%apor "ressure will &e less t'an # mm Kg according to (igure "+..!#
)iodegrada&ilit0 Inde, C 3.3-
8'is c'oice satisies all o t'e constraints on t'e solvent design.

=. Magnitude of effect on +oiling (oint of grou( contri+utions for the follo/ing grou(s: 7#$ 7C#
.
$
7Cl 9ali(hatic:.
!5K ;#$6.-.:R!Cl ;6-.63:R! CK
3
;-#.67:
Reasoning: '0drogen &onding 'as a larger inluence on &oiling point t'an molecular mass.

'&. Magnitude of effect on "o/ of grou( contri+utions for the follo/ing grou(s: 7#$ 7C#
.
$ 7Cl
9ali(hatic:.
!CK
3
;$.+2.3: R !Cl ;$.3-$#: R !5K ;!#.2$67:
Reasoning: !CK
3
and !Cl groups are '0drop'o&ic and is '0drop'0lic.

-6
Cha(ter 5. Evaluating E1(osures

'. Steady Eva(oration Rate of Ethyl+en3ene !rom a Pool of 6i>uid into a Room.

/ C 7..6,#$
!+

;>D
$.733
);%":S;# @ >DG#@ -6:
$.-+
T;v
$.-+
:
;8
$.$+
:;,
$.+
:;"
$.+
:
w'ere
/ is t'e evaporation rate ;g@sec!cm
-
:
>D is t'e molecular weig't o t'e evaporating species ;g@mole: C #$6 g@mole or et'0l&enJene
%" is t'e vapor pressure o t'e evaporating contaminant ;atm:
v is t'e air velocit0 parallel to t'e surace o t'e evaporating li9uid ;cm@sec: C +$ cm@s
8 is t'e surace temperature o t'e evaporating li9uid ;HE: C -66.7 HE
, is t'e lengt' o t'e evaporating pool in t'e direction o airlow ;cm: C ##3 cm or a # m
-
circular pool
o li9uid.
" is t'e am&ient pressure ;atm: C # atm.
)oiling "t., rom e9n. +!#,
8
&
;E: C #67.- G n
i
g
i
group g
i
contri&ution
# aaC 3$..6 ;a su&stituted car&on &ound to - aromatic car&ons:
+ aaCK +;-7.+3:
!CK
3
-#.67
RCK
-
-2.--
8
&
;E: C #67.- G -#.67 G -2.-- G +;-7.+3: G 3$..6 C 2#..7# E estimated
8
&
;corrected: C 8
&
= 62.72 G $.++..8
&
= $.$$$..$+;8
&
:
-
S8
&
.$$ET ;E9n. +!-:
C 2#..7# = 62.72 G $.++..;2#..7#: = $.$$$..$+;2#..7#:
-
C 2-#.27 E
8
&
;actual: C 2$6.#+ E
%apor pressure ;"
vp
::
ln "
vp
C SA;8
&
= C:
-
T U S#@;8
&
= C: ! #@;8 = C:T ;E9n. +!.:
S$.6. R 8
&
T
A C E
(
;7..+ G R ln 8
&
: C #.$6;7..+ G #.67. ln;2$6.#+:: C -$..
C C !#7 G $.#6 8
&
C !#7 G $.#6;2$6.#+: C +6..2
ln "
vp
C S-$.. ;2$6.#+= +6..2:
-
T U S#@;2$6.#+ = +6..2: ! #@;-66.7- = +6..2:T C !2.#7
S$.6. ;#.67.: ;2$6.#+:T
"
vp
C e,p;!2.#7: C #.+3,#$
!-
atm
-.

/ C 7..6,#$
!+

;>D
$.733
);%":S;# @ >DG#@ -6:
$.-+
T;v
$.-+
:
;8
$.$+
:;,
$.+
:;"
$.+
:
/ C ;7..6,#$
!+
:;#$6:
.733
;#.+3,#$
!-
:S;#@#$6G#@-6:
.-+
T;+$:
.-+
T@;;-66.7 E:
.$+
;##3:
.+
;#:
.+
:
C +.63,#$
!6
g@sec@cm
-
8'e total volatiliJation rate C /,A, w'ere A is ;# m
-
:;#$
2
cm
-
@ m
-
: C #$
2
cm
-
.
C ;+.63,#$
!6
g@sec@cm
-
:; #$
2
cm
-
: C $.$+63 g@sec

%. Estimate the Steady7State Concentration for the Emission Source in Pro+lem '.
C C Co G /@;k Z:, w'ere C is t'e concentration in t'e room, k is t'e mi,ing actor ;.+ or average
ventilation and $.# or poor ventilation:, and Z is t'e volumetric low rate ;$.+ m@s , 2 m , -.2+ m C 2.6
m
3
@s:.
Average ventilation:
C C $ G ;$.$+63 g@s:@;;$.+:;2.6 m
3
@s:: C $.$-3$ g@ m
3
.
"oor ventilation:
C C $ G ;$.$+63 g@s:@;;$.#:;2.6 m
3
@s:: C $.##+ g@ m
3
.
"EL C #$$ ppm
Converting to mass concentration:

i
C
;ppm:;>D:
;--.2 L@ mole:
10
6
C
;#$$:;#$6 g @ mole:
;--.2 L @ mole:
10
6
C 2..3,#$
!2
g @ L C 2..3,#$
!#
g @ m
3
)ot' o t'e calculated concentrations in t'e room are less t'an t'e "EL, so t'e e,posure is sae.

.. Confirm that e>uation 5.%.. is the solution to e>uation 5.%.' for a transient emission source.
*'ow t'at

C C C
o
G
/
kZ
;#! e,p;!kZt @ %::
e9uation 6.-.3
is t'e solution to t'e mass &alance e9uation or a room

%
dC
dt
C / ! kZ;C! C
o
) e9uation 6.-.#
w'ere
C is t'e concentration o air&orne contaminant in t'e work area ;mass@lengt'
3
:
% is t'e volume o t'e work area ;lengt'
3
:
t is t'e time during w'ic' t'e contaminant 'as &een emitted,
/ is t'e emission rate o t'e contaminant to t'e air ;mass@time:,
Z is t'e ventilation rate in t'e work area ;lengt'
3
@time:
-7
k is a mi,ing actor to account or incomplete mi,ing in t'e work area ;unitless:
C
o
is t'e concentration o t'e air&orne contaminant entering t'e work area ;mass@ lengt'
3
:.
*olution: Rearranging e9uation 6.-.#,

dC
dt
G
kZ
%
C C
;/ G kZC
o
)
%
An integrating actor
e
kZ@ % dt
C e
kZ@ % t
multiplies &ot' sides o t'e e9uation a&ove 0ielding,

d
dt
;e
kZ@ % t
)C
[ ]
C ;e
kZ@ % t
)
;/ G kZC
o
)
%
>ultipl0ing &ot' sides &0 dt and integrating results in,

d ;e
kZ@ % t
)C
[ ]
C ;e
kZ@ % t
)
;/ G kZC
o
)
%
dt
C
;/ G kZC
o
)
%
;e
kZ@ % t
) dt
or constant / and C
o
. 8'e solution to t'is is,

;e
kZ@ % t
)C C
;/ G kZC
o
)
%
;e
kZ@ % t
)
%
kZ
G Constant C
/
kZ
G C
o

_
,

;e
kZ@ % t
) G Constant
)ot' sides o t'e e9uation a&ove is divided &0 t'e integrating actor, 0ielding

C C
/
kZ
G C
o

_
,

G Constant ;e
!kZ@ % t
)
and evaluated at t'e initial condition o C C C
o
w'en t C $.

C
o
C
/
kZ
G C
o

_
,

G Constant ;e
!kZ@ % $
) Constant C !
/
kZ
8'e solution is t'en e9uation 6.-.3

C C
/
kZ
G C
o

_
,

!
/
kZ
;e
!kZ@ % t
) C C
o
G
/
kZ
[1 ;e
!kZ@ % t
)]

0. Derive e>uation 5.%.;$ /hich descri+es ventilation of a t/o7com(artment room. Descri+e ho/ you
/ould e1tend the analysis to a three com(artment room.
8'e conceptual model o t'e two compartment room is s'own in t'e sc'ematic diagram &elow in cross
section. 8'e concentration in compartment # is C
#
and in t'e larger compartment - is C
-
. >ass is input
-6
into compartment # at a rate / ;mass@time: and mass e,c'ange occurs &etween t'e compartments at a rate
o ) ;lengt'
3
@time:. 8'e ventilation rate o compartment - is Z ;lengt'
3
@time:.
At stead0!state,
Compartment #: $ C / = );C
#
= C
-
:
Compartment -: $ C );C
#
= C
-
: = Z C
-
$ C /= Z C
-
or C
-
C /@Z
Bow compartment # again: $ C / = );C
#
= C
-
: C / = );C
#
= /@Z:
*olving or C
#
: ) C
#
C / G )/@Z
C
#
C /@) G /@Z C /;#@) G #@Z: C /;)GZ:@;)Z:
(or a t'ree compartment, a similar anal0sis would occur using t'e ollowing diagram as a conceptual
model.

2. Assume that the room descri+ed in (ro+lems ' and % is characteri3ed as a cu+e$ '.2 meter on
each side centered over the (ool of ethyl+en3ene$ that e1changes air at a rate of ' m
.
?s /ith the rest
of the room. Develo( e1(ressions for the transient and steady state concentrations of ethyl+en3ene
in the air immediately a+ove the (ool$ and in the rest of the room.
At stead0!state,
Compartment #: $ C / = );C
#
= C
-
:
Compartment -: $ C );C
#
= C
-
: = Z C
-
$ C /= Z C
-
or C
%
@ G?A
3$
G
C1
B
C2
Co!0
G
C1
B1
C2
Co!0
C3
B2
Bow compartment # again: $ C / = );C
#
= C
-
: C / = );C
#
= /@Z:
*olving or C
#
: ) C
#
C / G )/@Z
C
'
@ /@) G /@Z C /;#@) G #@Z: C G9,BA:?9,A:
C
#
C /;)GZ:@;)Z: C ;.$+63 g@s:;# m
3
@s G 2.6 m
3
@s:@;;# m
3
@s:;2.6 m
3
@s:: C $.$6.7 g@m
3
.
C
-
C /@Z C ;$.$+63 g@s:@;2.6 m
3
@s: C $.$##+ g@m
3
.

5. Estimate the dermal and inhalation e1(osures that might +e associated /ith collecting a sam(le
of ethyl+en3ene from the (ool descri+ed in (ro+lems '$ % and 2. Ma4e reasona+le assum(tions
a+out the time re>uired to collect the sam(le and inhalation rates. )s dermal or inhalation the
dominant e1(osure routeC
1ermal e,posure:
1A C ;*:;Z:;B:;D(:;A)*: E9uation 6.-.#$
w'ere
1A is t'e dermal a&sor&ed dose rate o t'e c'emical ;mass@time:,
* is t'e surace area o t'e skin contacted &0 t'e c'emical ;2-$ cm
-
: = assume one 'and
Z is t'e 9uantit0 deposited on t'e skin per event ;-.# mg@cm
-
@event:,
B is t'e num&er o e,posure events per da0 ;# event@da0:,
D( is t'e weig't raction o t'e c'emical o concern in t'e mi,ture ;#.$:, and
A)* is t'e raction o t'e applied dose a&sor&ed during t'e event ;#.$:.
1A C ;2-$ cm
-
:;-.# mg@cm @event:;# event:;#.$:;#.$: C 77- mg@da0
In'alation e,posure:
In'A C ;C#:;CR:;C1:
In'A is t'e in'alation a&sor&ed dose rate o t'e c'emical ;mg@da0:
C# is t'e concentration o et'0l&enJene in t'e air a&ove t'e pool ;mg@m3:
CR is t'e contact rate ;#$ m
3
&reat'ed@'r:
C1 is t'e contact duration ;7 'r@da0:
In'A C ;$.$6.7 g@m
3
:; #$ m
3
&reat'ed@'r: ;7 'r@da0: C +.2 g@da0 C +,2$$ mg@da0.
In'alation is t'e dominant e,posure route.

;. E1(osure to Acrolein and Methyl Ethyl "etone from 6ea4ing E>ui(ment
Z C ventilation rate C -$$ m
3
@'r[
Acrolein: ;-!"ropenal: C
3
K
2
5 ;>DC+6.$6:
*olution data 2 A;wt: acrolein in water
Leak rate # milliliter solution@min
/
acrolein
, Emission rate to air ;# ml solution@min:;# g soln@ml:;$.$2 g acrolein@g soln:;6$ min@'r: C -.2 g
acrolein@'r
3#
C
acrolein
C /
acrolein
@;kZ: C ;-.2 g@'r:@;;$.+:;-$$ m
3
@'r:: C $.$-2 g acrolein@m
3
"EL
acrolein
C $.# ppm

i
C
;ppm:;>D:
;--.2 L@ mole:
10
6
C
;$.#:;+6.$6 g @ mole:
;--.2 L @ mole:
10
6
C -.+,#$
!.
g @ L C -.+,#$
!2
g @ m
3
)ecause t'e predicted concentration o acrolein in air ;$.$-2 g@m
3
: is greater t'an t'e allowa&le workplace
concentration derived rom t'e "EL ;-.+,#$
!2
g@m
3
:, t'is release poses a danger to people in t'e
workplace.
>et'0l Et'0l Eetone ;>EE:: ;-!&utanone: C
2
K
7
5 ;>DC.-.##:
*olution data + A;wt: met'0l et'0l ketone in water
Leak rate 3$ milliliter solution@min
/
>EE
, Emission rate to air ;3$ ml solution@min:;# g soln@ml:;$.$+ g >EE@g soln:;6$ min@'r: C 6$.$ g
>EE@'r
C
>EE
C /
>EE
@;kZ: C ;6$ g@'r:@;;$.+:;-$$ m
3
@'r:: C $.6$ g >EE@m
3
"EL
acrolein
C -$$ ppm

i
C
;ppm:;>D:
;--.2 L@ mole:
10
6
C
;-$$:;.-.## g @ mole:
;--.2 L @ mole:
10
6
C 6.22,#$
!2
g @ L C 6.22,#$
!#
g @ m
3
)ecause t'e predicted concentration o >EE in air ;$.6$ g@m
3
: is greater t'an t'e allowa&le workplace
concentration derived rom t'e "EL ;$.622 g@m
3
:, t'is release poses a danger to people in t'e workplace.

<. Dse the Green Chemistry E1(ert System 9///.e(a.gov?greenchemistry?gces.htm: to identify
structural modifications that can +e made to nitriles to reduce their to1icity.
8'e ollowing comments were e,tracted rom t'e /reen C'emistr0 E,pert *0stem.
Bitriles are organic su&stances t'at contain t'e c0ano ;CB: group. Certain nitriles are 9uite potent in
causing acute let'alit0 in 'umans and animals. As a class nitriles var0 &roadl0 in t'eir a&ilit0 to cause
acute let'alit0, and su&tle dierences in structure can dramaticall0 aect to,ic potenc0. It 'as &een
o&served t'at e,posure o 'umans and e,perimental animals to t'e more acutel0 to,ic nitriles results in
signs and s0mptoms similar to t'at o c0anide poisoning, implicating ree c0anide as t'e cause o
let'alit0. C0anide release rom nitriles results rom t'eir enJ0matic meta&olism in t'e liver, ollowing
e,posure and su&se9uent a&sorption. In t'e liver, t'e meta&olism o nitriles involves '0dro,0lation o
one o t'e alip'atic car&on atoms &0 c0toc'rome "2+$ enJ0mes. C0toc'rome "2+$!mediated
'0dro,0lation o t'e car&on atom alp'a ;i.e., adPacent: to t'e c0ano group 0ields a c0ano'0drin
intermediate, w'ic' rapidl0 decomposes to li&erate c0anide and t'e corresponding car&on0l compound.
(or e,ample acetonitrile is not ver0 acutel0 let'al ;mouse oral L1+$ C 6.++ mmol@kg: w'ereas its
'omolog propionitrile is ten!old greater in to,icit0 ;L1+$ C $.6+ mmol@kg:. Large dierences in to,icit0
are known or ot'er nitriles.
3-
#. #hen de%i-nin- a nit!ile) add %t!uctu!al featu!e% that 0ill p!e&ent o! (ini(i3e cytoch!o(e .45"2
(ediated hyd!oxylation at the alpha2ca!+on6 5ne strateg0 is to place a '0dro,0l group on a car&on
remote rom t'e alp'a car&on. 8'is will divert C0toc'rome "2+$!mediated '0dro,0lation awa0 rom t'e
alp'a car&on, t'us reducing c0anide release.
-. 7nle%% a+%olutely nece%%a!y fo! intended u%e) do not add hyd!oxy o! a(ino -!oup% (%u+%tituted o!
un%u+%tituted) to the alpha2ca!+on) +ecau%e the%e nit!ile% 0ill +e hi-hly acutely toxic6
3. #hen con%ide!in- %t!uctu!al (odification% that a!e intended to !educe acute toxicity (lethality)) +e
ca!eful not to choo%e and inco!po!ate %t!uctu!al (odification% that 0ill !educe acute toxicity) +ut 0ill
+e%to0 o%teolathy!i%(6

=. )n designing chemicals that /ill minimi3e human u(ta4e$ you may /ish to consider (ro(erties
such as volatility$ octanol7/ater (artition coefficient and /ater solu+ility. !or high$ medium and
lo/ values of each of these (arameters$ characteri3e /hether e1(osure due to inhalation$ ingestion$
and dermal contact are li4ely to +e im(ortant.
Dater *olu&ilit0
E,posure Route Kig' Dater *olu&ilit0 >oderate Dater
*olu&ilit0
Low Dater *olu&ilit0
In'alation "otentiall0 'ig'
uptake
Lower uptake rate Lower uptake rate
Ingestion Lower uptake due to
poor mass transer
wit'in g.i. tract
"otentiall0 'ig'
uptake
Low uptake due to
poor mass transer
wit'in g.i. tract
1ermal Contact Lower uptake due to
poor mass transer
t'roug' t'e skin
"otentiall0 'ig'
uptake
Low uptake due to
poor mass transer
t'roug' t'e skin
%olatilit0
E,posure Route Kig' %olatilit0 >oderate %olatilit0 Low %olatilit0
In'alation "otentiall0 'ig'
uptake
"otentiall0 lower
uptake rate
Low uptake rate
Ingestion Low uptake rate Low uptake rate "otentiall0 'ig'
uptake rate i
moderatel0 water
solu&le
1ermal Contact "otentiall0 low uptake "otentiall0 low uptake "otentiall0 low uptake
5ctanol!Dater "artition Coeicient
E,posure Route Kig' Eow >oderate Eow Low Eow
In'alation "otentiall0 low uptake "otentiall0 low uptake
rate
"otentiall0 'ig'
uptake rate
Ingestion Lower uptake due to
poor mass transer
"otentiall0 'ig'
uptake
Low uptake due to
poor mass transer
33
wit'in g.i. tract wit'in g.i. tract
1ermal Contact Lower uptake due to
poor mass transer
t'roug' t'e skin
"otentiall0 'ig'
uptake
Low uptake due to
poor mass transer
t'roug' t'e skin

'&. E1(osure to #a3ardous Chemicals from a Primer Production !acility
a: *ources o 5ccupational E,posure
Reactor #: In'alation e,posure during cleanout
1ermal e,posure during sampling and cleanout
(iltration: 1ermal e,posure during disposal o spend ilters
Reactor -: In'alation e,posure during cleanout
1istillation: 1ermal e,posure during sampling
>i,er: In'alation e,posure during cleanout
&: *ources o Releases to t'e Environment
Reactor #: Releases to air, water, and@or land rom cleanout
Releases to water or land during sampling
(iltration: Releases to land during spent ilter disposal
Reactor -: Releases to air, water, and@or land rom cleanout
1istillation: Releases to air due to e,cess solvent treatment or disposal
>i,er: Releases to air, water, and@or land rom cleanout

''. E1(osure to #a3ardous Chemicals from the Coloring of 6eather and Dyes
a: *ources o 5ccupational E,posure
Deig'ing: In'alation e,posure during weig'ing o d0e dust
1issolving: In'alation e,posure during cleanout
"ump: 1ermal e,posure during cleanout
10eing: In'alation e,posure during cleanout
1r0er: In'alation e,posure during venting o 'eated air
&: *ources o Releases to t'e Environment
Deig'ing: Releases to air ater puriication ilters
1issolving: Releases to air, water, and@or land rom cleanout
"ump: Releases to air during cleanout
10eing: Releases to air due to e,cess spent solution treatment or disposal
32
Releases to air, water, and@or land rom cleanout
8ranser: Release to air during transer
1r0er: Releases to air during venting
3+
Cha(ter ;. Green Chemistry

'. Atom and Mass Efficiency Calculations: Calculate mass and atom efficiencies
a: ;Addition reaction: Iso&ut0lene G met'anol met'0l,tert!&ut0l et'er
C
2
K
7
G CK
3
5K ;C
2
K
6
:!5!CK
3
>ass eicienc0: (eedstocks = +;#-: G #-;#: G #;#6: C 77
"roduct = +;#-: G #-;#: G #;#6: C 77 QQ.. eicienc0 C #$$A
Car&on eicienc0: (eedstocks = +;#-: C 6$
"roduct = +;#-: C 6$ QQ.. eicienc0 C #$$A
K0drogen eicienc0: (eedstocks = #-;#: C #-
"roduct = #-;#: C #- QQ.. eicienc0 C #$$A
5,0gen eicienc0: (eedstocks = #;#6: C #6
"roduct = #;#6: C #6 QQ.. eicienc0 C #$$A
&: ;*u&stitution reaction: "'enol G ammonia aniline G water
C
6
K
+
!5K G BK
3
C
6
K
+
!BK
-
G K
-
5
>ass eicienc0: (eedstocks = 6;#-: G 6;#: G #;#6: G #;#2: C ###
"roduct = 6;#-: G .;#: G $;#6: G #;#2: C 63 QQ.. eicienc0 C 73.7A
Car&on eicienc0: (eedstocks = 6;#-: C .-
"roduct = 6;#-: C .- QQ.. eicienc0 C #$$A
K0drogen eicienc0: (eedstocks = 6;#: C 6
"roduct = .;#: C . QQ.. eicienc0 C ...7A
"roduct = $;#6: C $ QQ.. eicienc0 C $A
Bitrogen eicienc0: (eedstocks = #;#2: C #2
c: ;Elimination reaction: Et'0l&enJene st0rene G '0drogen
C
6
K
+
!C
-
K
+
C
6
K
+
!C
-
K
3
G K
-
>ass eicienc0: (eedstocks = 7;#-: G #$;#: C #$6
"roduct = 7;#-: G 7;#: C #$2 QQ.. eicienc0 C 67.#A
Car&on eicienc0: (eedstocks = 7;#-: C 66
"roduct = 7;#-: C 66 QQ.. eicienc0 C #$$A
K0drogen eicienc0: (eedstocks = #$;#: C #$
"roduct = 7;#: C 7 QQ.. eicienc0 C 7$A
d: 5t'er industriall0 important e,amples o additions, su&stitutions, and elimination reactions ;see
Dittkco, K.A. and Reu&en, )./. <Industrial 5rganic C'emicals?, \o'n Dile0 & *ons, Bew ]ork, #666W
and Deissermel, E. and Arpe, K.!\. <Industrial 5rganic C'emistr0?, %CK %erlagsgesellsc'at m&K a
Dile0 compan0, Dein'eim /erman0, #66.:.
Addition Reactions:
36
Et'anol rom et'ene
CK
-
CCK
-
G K
-
5 C
-
K
+
5K ;'0dration o et'0lene using a p'osp'oric acid catal0st, low per pass
conversions on t'e order o #$A:
>ass eicienc0: (eedstocks = -;#-: G 6;#: G #;#6: C 26
"roduct = -;#-: G 6;#: G #;#6: C 26 QQ.. eicienc0 C #$$A
Car&on eicienc0: (eedstocks = -;#-: C -2
"roduct = -;#-: C -2 QQ.. eicienc0 C #$$A
"roduct = 6;#: C 6 QQ.. eicienc0 C #$$A
Et'0lene o,ide rom et'ene
CK
-
CCK
-
G $.+5
-
CK
-
^CK
-
;silver catal0st, #+ &ar and -+$HC, 0ield R 7$A:
[ @
5
>ass eicienc0: (eedstocks = -;#-: G 2;#: G #;#6: C 22
"roduct = -;#-: G 2;#: G #;#6: C 22 QQ.. eicienc0 C #$$A
"roduct = 2;#: C 2 QQ.. eicienc0 C #$$A
%in0l c'loride rom acet0lene
CKCK G KCl CK
-
CCKCl
>ass eicienc0: (eedstocks = -;#-: G 3;#: G #;3+.2+: C 6-.2+
"roduct = -;#-: G 3;#: G #;3+.2+: C 6-.2+ QQ.. eicienc0 C #$$A
K0drogen eicienc0: (eedstocks = +;#: C +
"roduct = +;#: C + QQ.. eicienc0 C #$$A
C'lorine eicienc0: (eedstocks = #;3+.2+: C 3+.2+
"roduct = #;3+.2+: C 3+.2+QQ.. eicienc0 C #$$A
*u&stitution Reactions:
%in0l c'loride rom et'ene
CK
-
CCK
-
G Cl
-
CK
-
ClCK
-
Cl CK
-
CCKCl G KCl
>ass eicienc0: (eedstocks = -;#-: G 2;#: G -;3+.2+: C 67.2+
"roduct = -;#-: G 3;#: G #;3+.2+: C 6-.2+ QQ.. eicienc0 C 63.2A
"roduct = 3;#: C 3 QQ.. eicienc0 C .+A
3.
C'lorine eicienc0: (eedstocks = -;3+.2+: C .$.6
"roduct = #;3+.2+: C 3+.2+QQ.. eicienc0 C +$A
C'lorine rom o,idation o KCl
2KCl G 5
-
-K
-
5 G -Cl
-
>ass eicienc0: (eedstocks = 2;#: G 2;3+.2+: G #;3-: C -#..7
"roduct = -;.$.6: C #2#.7 QQ.. eicienc0 C 6+.#A
"roduct = $;#: C $ QQ.. eicienc0 C $A
C'lorine eicienc0: (eedstocks = 2;3+.2+: C #2#.7
"roduct = -;.$.6: C #2#.7 QQ.. eicienc0 C #$$A
5,0gen eicienc0: (eedstocks = #;3-: C 3-
"roduct = $;3-: C $ QQ.. eicienc0 C $A
%in0l c'loride rom et'0lene using o,0c'lorination ;)0 integrating t'e a&ove two reactions, we can
increase t'e mass eicienc0 o t'e overall production o vin0l c'loride:
>ass eicienc0: (eedstocks = 6;#-: G #+;#: G 6;3+.2+: G #.+;#6: C 333..
"roduct = 6;#-: G #+;#: G 6;3+.2+: G $;#6: C 3$6..QQ.. eicienc0 C 6-.7A
Car&on eicienc0: (eedstocks = 6;#-: C .-
"roduct = 6;#-: C .- QQ.. eicienc0 C #$$A
K0drogen eicienc0: (eedstocks = #+;#: C #+
"roduct = #+;#: C #+ QQ.. eicienc0 C #$$A
C'lorine eicienc0: (eedstocks = 6;3+.2+: C ---..
"roduct = 6;3+.2+: C ---.. QQ.. eicienc0 C #$$A
5,0gen eicienc0: (eedstocks = #.+;#6: C -2
"roduct = $;#6: C $ QQ.. eicienc0 C $A
Elimination Reactions:
"'enol rom de'0drogenation o a c0clo'e,anone@c0clo'e,anol mi,ture
37
#.+CK-CCK- G #.+Cl- #.+CK-ClCK-Cl
#.+CK-CCK- G 3KCl G $..+5-
#.+CK-ClCK-Cl G #.+K-5
3CK-ClCK-Cl 3CK-CCKCl G 3 KCl
5K
C5G
5K
G 6@- K
-
-
>ass eicienc0: (eedstocks = #-;#-: G ##;#: G -;#6: C #7.
"roduct = #-;#-: G -;#: G -;#6: C #.7 QQ.. eicienc0 C 6+.-A
Car&on eicienc0: (eedstocks = #-;#-: C #22
"roduct = #-;#-: C #22 QQ.. eicienc0 C #$$A
K0drogen eicienc0: (eedstocks = ##;#: C ##
"roduct = -;#: C - QQ.. eicienc0 C #7.-A
5,0gen eicienc0: (eedstocks = -;#6: C 3-
"roduct = -;#6: C 3- QQ.. eicienc0 C #$$A

%. Confirm mass efficiencies in Ta+le ;.'
>n5
-
:
>ass eicienc0: (eedstocks = #;+2.62: G -;#6: C 76.62
"roduct = #;#6: C #6 QQ.. eicienc0 C #7.2A
"'I5:
>ass eicienc0: (eedstocks = #;3$.6.: G #;#: G #;#-6.6: G #;#6: C #.2.6
"roduct = #;#6: C #6 QQ.. eicienc0 C 6.-A
K
-
5
-
:
>ass eicienc0: (eedstocks = -;#: G -;#6: C 32
"roduct = #;#6: C #6 QQ.. eicienc0 C 2..$A
t!)u55K: ;CK
3
!CK
-
!CK
-
!C55K:
>ass eicienc0: (eedstocks = 2;#-: G 7;#: G -;#6: C 77
"roduct = #;#6: C #6 QQ.. eicienc0 C #7.-A
Ba5Cl:
>ass eicienc0: (eedstocks = #;--.66: G #;#6: G #;3+.2+: C .2.22
"roduct = #;#6: C #6 QQ.. eicienc0 C -#.+A
36
E
-
Cr
-
5
.
:
>ass eicienc0: (eedstocks = -;36.#: G -;+-: G .;#6: C -62.-
"roduct = 2;#6: C 62 QQ.. eicienc0 C -#.7A
E>n5
2
:
>ass eicienc0: (eedstocks = #;36.#: G #;+2.62: G 2;#6: C #+7.$
"roduct = -;#6: C 3- QQ.. eicienc0 C -$.-A

2$
Cha(ter <. Evaluating Environmental Performance During Process Synthesis

'. Com(are the car+onylation of dinitrotoluene and the amine7(hosgene routes for the (roduction
of toluene diisocyanate 9TD): using a Tier ' economic and environmental (erformance evaluation.
A(ine 2 pho%-ene !oute8
C
6
K
3
;CK
3
:;BK
-
:
-
G - C5Cl
-
C
6
K
3
;CK
3
:;!BCCC5:
-
G 2 KCl
a!+onylation of nit!o+en3ene8
C
6
K
3
;CK
3
:;B5
-
:
-
G 6 C5 C
6
K
3
;CK
3
:;!BCCC5:
-
G 2 C 5
-
8a&le o stoic'iometric and to,icit0 data or eac' reaction pat'wa0
En&i!on(ental and Econo(ic E&aluation
Environmental evaluation

8L% Inde, C
i
i
TLV
i
1
;"EL can &e used instead o 8L%: ;E9uation 7!-:

E"A Inde, C
i
i
(ma,imum o oral and in'alation weig'ting actor:

i
;E9uation 7!3:
Amine!p'osgene route
8L% Inde, C ;..6:;#@.#:G;.$#:;#@3+$:G;.2:;#@.:G;#.-6:;#@.2:G;#:;#@.#2: C #..6+
E"A Inde, C ;.$#:;#$$:G;.2:;#$$:G;#:;#$$,$$$: C #$$,$2#
2#
Cost o Raw >aterials C ;..6:;.+.6:G;.$#:;.++$:G;#.-6:;.6#$: C _#.-#@l& 81I
Car&on0lation Route
8L% Inde, C ;#.$2:;#@#.+:G;#:;#@++:G;#:;#@.#2:G;#:;#@6$$$: C ..7+
E"A Inde, C ;#.$2:;#,$$$:G;#:;#$$,$$$: C #$#,$2$
Cost o Raw >aterials C ;#.$2:;.36+:G;#:;.$2: C _$.2-@l& 81I
1iscussion: 8'e 8L% Inde, indicates t'at t'e car&on0lation route is superior to t'e amine!p'osgene route.
8'e E"A Inde, indicates t'at &ot' routes are a&out t'e same, &ut data is lacking or t'is inde,, so we
s'ould rel0 less on t'is inde,. 8'e cost anal0sis indicates t'at t'e car&on0lation route is superior.

%. Tier % environmental assessment for the (roduction of maleic anhydride 9MA: from n7+utane.
a: Emission sources
#. %enting rom t'e crude >A and reined >A product storage tanks
-. Reactor emissions
3. A&sor&er column o!gas
2. %acuum *tripper
+. *olvent puriication ;distillation column:
6. )atc' distillation
.. )oiler emissions
7. (ugitive emissions
&: Estimate wastes and emissions or t'e processes
>A storage tanks, one tank or crude >A and one or reined >A. *ince crude >A is 66.7A pure, we
assume pure >A or t'is emission estimation. 8o proceed, assume t'at t'e process produces +$,$$$ tons
>A@0r, w'ic' is t'e t'roug'put or t'e tanks. 8o use t'e 8ABE* sotware, t'e volumetric low rate is
needed in gallons@0r. 8'e densit0 o >A is #-.32 l& >A@gal >A, so t'e volumetric low rate is 7.#,#$
6

gal >A@0r. A turnover rate o -!3 da0s or t'e tank is assumed, so t'e tank working volume s'ould &e
a&out 6.,+$$ gal. A tank wit' a diameter o -7 t and 'eig't o #+ t will work or t'is volume o tank.
De assume a vertical i,ed!roo tank wit' no pollution control o w'ite color in good condition. Also, t'e
average li9uid 'eig't is #3 t and t'e ma,imum is #2.6+ t. )ecause t'e 8ABE* sotware does not 'ave
data or >A, we c'oose a surrogate compound wit' a similar vapor pressure ;$.# psia at am&ient
conditions:, #,#,#,-!tetrac'loroet'ane. 8'e annual emissions are #,3+6 l&@0r or eac' tank 0ielding an
emission per unit o >A production o #,3+6 l& >A@0r@;;+$,$$$ tons >A@0r:;#$
3
l& >A@$.+ ton >A: C
$.$#36 l& >A@#$
3
l& >A. (or &ot' tanks, t'e total tank emissions o >A is -;$.$#36 l& >A@#$
3
l& >A:
C $.$-.# l& >A@#$
3
l& >A.
Reactor Emissions: 8'e reactor is a packed &ed o small diameter tu&es illed wit' catal0st. De assume
t'ere are no emissions rom t'e reactor directl0, &ut will include t'e reactor in t'e estimation o ugitive
emissions rom t'e process. (or lack o inormation, we assume no catal0st!related waste generation.
A&sor&er column o!gas: 8'e a&sor&er oil is 'ig'l0 selective or >A, &ut is not selective or t'e reactants
n!&utane and air and t'e &0products C5 and C5
-
. De assume t'ereore t'at reaction stoic'iometr0
dictates emissions rom t'e a&sor&er. According to literature sources ;Eirk ! 5t'mer Enc0clopedia o
C'emical 8ec'nolog0, %ol. #+, pg 6#$:, t0pical conversions o n!&utane are 7+A and 0ields o >A are
2-
+$!6$A on a molar &asis. (or +$,$$$ tons >A@0r, molar low rate o product is #.$-,#$
6
l&mole >A@0r.
n!&utane eed rate is #.$-,#$
6
@$.7+ C #.-,#$
6
l&mole n!&utane@0r or +..6,#$
6
l& n!&utane@0r.
n!&utane emission rate rom t'e a&sor&er is $.#+;#.-,#$
6
l&mole n!&utane@0r: C $.#7,#$
6
l&mole n!
&utane@0r or 7.62,#$
6
l& n!&utane@0r :@;;+$,$$$ tons >A@0r:;#$
3
l& >A@$.+ ton >A: C 76.2 l& n!
&utane@#$
3
l& >A.
Assuming t'at 0ield o >A is 6$A on a molar &asis and t'at &0product ormation is e9uall0 split &etween
C5 and C5
-
, reaction stoic'iometr0 will dictate emissions o t'ese &0products rom t'e a&sor&er column.
Reactions or C5 and C5
-
are
C
2
K
#$
G 6.+ 5
-
2 C5
-
G + K
-
5
C
2
K
#$
G 2.+ 5
-
2 C5 G + K
-
5
>olar emission rates or eac' &0product are ;2:;-$A: o t'e molar >A product low rate, ;2:;$.-:
;#.$-,#$
6
l&mole >A@0r: C 7.#6,#$
+
l&mole C5 or C5
-
@0r. Converting to mass emission rates or eac'
results in, or C5
-
, 22;7.#6,#$
+
l&mole@0r:@;;+$,$$$ tons >A@0r:;#$
3
l& >A@$.+ ton >A: C 3+6.- l&
C5
-
@#$
3
l& >A and or C5, -7;7.#6,#$
+
l&mole@0r:@;;+$,$$$ tons >A@0r:;#$
3
l& >A@$.+ ton >A: C
--7.2 l& C5
-
@#$
3
l& >A.
%acuum *tripper: According to t'e average emission actors or c'emical process units s'own in 8a&le
7.3.-, t'e emission rate o $.- l& >A@#$
3
l& >A.
*olvent "uriication Column: Little inormation is given regarding solvent puriication, &ut we ma0
assume t'at distillation o residual >A is separated rom t'e 'eavier a&sor&er solvent. According to
8a&le 7.3.-, distillation emissions are $.# l&@#$
3
l& >A and we assume t'at t'ese emissions are >A.
;Bote t'at t'ere is an error in t'e entr0 in 8a&le 7.3.- or distillation emission actor. 8'e correct actor
s'ould &e $.# not $..:.
)atc' 1istillation: 8'e emission rate or >A or &atc' distillation are again $.# l&@#$
3
l& >A.
)ioler Emissions:
8o estimate t'ese emissions, an estimate o energ0 consumption per mass o product is re9uired.
Rudd, et al., ;#67# in c'apter 7: provide estimates o energ0 consumption or a num&er o processes and
suggest a value o $.2# metric tons o uel oil e9uivalent per metric ton ;#$
3
kg: o product. Assuming t'at M6 uel oil wit' #A sulur is used and t'at no emission controls are in
place leads to estimates ;&ased on 8a&le 7.3!+: o:
*5
- emissions:
;#6 kg@#$
3
L uel oil:@;$.7 kg@L: ;2#$ kg uel oil@ #$
3
kg >A product: C 6.3 kg *5
- @#$
3
kg >A.
*5
3 emissions:
;$.66 kg@#$
3
L uel oil:@;$.7 kg@L: ;2#$ kg uel oil@#$
3
kg >A product: C $.33 kg *5
3 @#$
3
kg >A
B5, emissions:
;7 kg@#$
3
3
kg >A product: C 2.# kg B5, @ #$
3
kg >A
"articulate >atter emissions:
;#.+ kg@#$
3
3
kg >A product: C $.7 kg "> @ #$
3
kg >A
Car&on >ono,ide emissions:
;$.6 kg@#$
3
3
kg >A product: C $.3 kg C5 @#$
3
kg >A
Car&on 1io,ide emissions:
;3,$-+ kg@#$
3
3
kg >A product: C #,++$.3 kg C5
- @#$
3
kg >A
23
(ugitive emissions:
8o accuratel0 estimate ugitive emissions re9uires a count o valves, langes, ittings, pumps
and ot'er devices t'at are used in t'e process. *uc' counts are not generall0 availa&le or
preliminar0 process designs, 'owever, roug' estimates can &e made &ased on e,perience.
80picall0, ugitive emissions or c'emical processes total $.+!#.+ kg per #$
3
kg product. In t'is case, we
'ave pro&a&l0 alread0 accounted or some o t'e ugitive emissions t'roug' t'e emission actors or t'e
reactors and distillation column, t'ereore, an estimate o $.+ kg per #$
3
kg product is appropriate, wit'
t'e emissions &eing primaril0 >A.
Loading and 4nloading Losses:
8'e loading and o!loading emissions can &e estimated using E9uation 7.3!2. Assuming a saturation
actor o $.6 ;8a&le 7.3.6:, a vapor pressure o $.-+ mm Kg or >A ;rom C'em(ate, t'e data&ase on t'e
*0racuse Researc' Corporation we& site ! see Appendi, (:, a molecular weig't o 67 and a temperature o
+3$ R gives a loading loss o : LL C #-.26 ;$.6U$.-+U;#2..@.6$:U67@+3$: C $.$$6. l&@#$
3
gal C +.2,#$
!2

l&@#$
3
l& product ;speciic gravit0 o >A is #.27:.
A summar0 o emissions is provided in t'e ta&le &elow ;kg emitted @ #$
3
kg >A:
Release Source Maleic
Anhydride
(MA)
n-butane Criteria
Pollutants
CO2
Venting from storage
tanks
0.027
Absorber column
86.4 228.4 "C#$ 359.2
Vacuum Stripper
0.2
Distillation Columns
0.2
Boiler emissions
9.3 "%#2$
0.3 "%#3$
4.1 "&#'$
0.8 "()$
0.3 "C#$
1*550.3
Fugitive
Emissions
0.5
Loading/unloading
operations
0.0005
Total .!" #$.% &%".& '(!!.)
22
Cha(ter =. Dnit (erations and Pollution Prevention

'. Solvent Choice for E1traction of Caffeine from Coffee ,eans
1ata or car&on dio,ide, et'0l acetate, and dic'loromet'ane can &e ound in >*1*s. A good we& site or
>*1*s is 'ttp:@@msds.pdc.cornell.edu@msdssrc'.asp
Compound Bame CA* Bum&er "EL ;ppm: L1
+$
;mg@kg: Cancer Eects
>et'0lene C'loride .+!$6!- +$$ -#36 #
Car&on 1io,ide #-2!37!6 +$$$ not known -
Et'0l Acetate #2#!.7!6 2$$ +6-$ 3
8ric'loroet'0lene .6!$#!6 #$$ 26$$ 2
#. >et'0ulene C'loride Cancer Eects
Carcinogenicit0 ! B8": ]E*
Carcinogenicit0 ! IARC: ]E*
Carcinogenicit0 ! 5*KA: B5
E,planation Carcinogenicit0: >E8K]LEBE CKL5RI1E: /R54" -);IARC:, /R54"
-;B8":.
-. Carcinogenicit0 ! B8": B5
Carcinogenicit0 ! IARC: B5
E,planation Carcinogenicit0: 8KI* C5>"54B1 C5B8AIB* B5 IB/RE1IEB8* A8
C5BCEB8RA8I5B* 5( $.#A 5R /REA8ER 8KA8 ARE CARCIB5/EB* 5R *4*"EC8
CARCIB5/EB*.
3. Carcinogenicit0 ! B8": B5
E,planation Carcinogenicit0: 8KERE ARE B5 IB/RE1IEB8* A)5%E $.#A DKICK ARE
I1EB8I(IE1 A* CARCIB5/EB* )] B8", IARC 5R 5*KA.
2. Carcinogenicit0 ! B8": B5
E,planation Carcinogenicit0: "ER >*1*:GCARC RE*"5B*E 5CC4RRE1 5BL] IB >ICE
/I%EB L/ 15*E*.1A8A *4//E*8 *K54L1 "5*E LI88LE@B5 CARC KA` (5R >AB.
8'e least preerred solvent is met'0lene c'loride &ecause t'e L1
+$
is t'e smallest and t'e cancer risk is
t'e greatest o t'e t'ree c'oices. 8'e most preera&le is car&on dio,ide &ecause t'e "EL is 'ig'est ;least
to,ic: and no cancer risk. Bote t'at it is &est to c'eck several >*1*s as variations and errors appear in
dierent compan0 reports.

2+
%. (timum Plug !lo/ Reactor *olume for a Series Reaction
8'e t'ree e9uations descri&ing t'e d0namics o t'e reacting s0stem are

r
A
dC
A
dt
k
1
C
A
and at t C $, C
A
C
Ao
r
B
dC
B
dt
k
1
C
A
k
2
C
B
and at t C $, C
B
0
r
C
dC
C
dt
k
2
C
B
and at t C $, C
C
0
Reactant concentration,
A
In t'is e9uation, we can separate varia&les directl0 and integrate.
dC
A
C
A
k
1
dt
. 8'e solution to t'is e9uation su&Pect to t'e initial condition is

C
A
C
Ao
e
k
1
t

"roduct concentration,
9
In t'is e9uation, we must su&stitute in or
A
rom t'e solution a&ove.
dC
B
dt
k
1
C
A
k
2
C
B
k
1
C
Ao
e
k
1
t
k
2
C
B
. I t'is e9uation is rearranged, t'e result is
dC
B
dt
+ k
2
C
B
k
1
C
Ao
e
k
1
t
. 8o solve t'is e9uation, we multipl0 &ot' sides &0 t'e integrating actor,
e
k
2
dt
e
k
2
t
. Ater multipl0ing and t'en simpli0ing, we arrive at an e9uation to integrate,
d(e
k
2
t
C
B
) k
1
C
Ao
e
( k
1
k
2
) t
dt

. Ater integrating and evaluating t'e integration constant using t'e initial
condition a&ove, t'e concentration o product is
C
B
C
Ao
k
1
(k
1
k
2
)
e
k
2
t
e
k
1
t
[ ]
.
Daste concentration,
8'e e9uation or
can &e solved using t'e result or product concentration a&ove,

dC
C
dt
k
2
C
B
k
2
C
Ao
k
1
(k
1
k
2
)
e
k
2
t
e
k
1
t
[ ], &0 irst separating varia&les and t'en integrating
dC
C
k
2
C
Ao
k
1
(k
1
k
2
)
e
k
2
t
e
k
1
t
[ ]

dt
. Ater evaluating t'e constant o integration, we get
C
C
k
2
C
Ao
k
1
(k
1
k
2
)
1
k
2
(1e
k
2
t
)
1
k
1
(1e
k
1
t
)

1
]
1 .
a: 8o ma,imiJe t'e 0ield o ), t'e volume o t'e reactor must &e suc' t'at t'e residence time in t'e
reactor is optimum. 8o determine t'is optimum reactor residence time, we must determine
dC
B
dt
0
and
solve or t'e residence time.

dC
B
dt
0 k
1
C
A
k
2
C
B
k
1
C
Ao
e
k
1
t
k
2
C
Ao
k
1
(k
1
k
2
)
e
k
2
t
e
k
1
t
[ ] . >ultipl0ing t'roug' &0 e
k
1
t
we get
26
0 k
1
C
Ao
k
2
C
Ao
k
1
(k
1
k
2
)
e
(k
1
k
2
)t
1
[ ], and simpli0ing urt'er
0 1
k
2
(k
1
k
2
)
e
(k
1
k
2
)t
1
[ ]and urt'er still
(k
1
k
2
)
k
2
e
(k
1
k
2
)t
1
[ ] until
ln
(k
1
k
2
)
k
2
+1

1
]
1
(k
1
k
2
)t
.
*olving or t'e residence time, we arrive at
t
ln
(k
1
k
2
)
k
2
+1

1
]
1
(k
1
k
2
)
ln
(0.2 0.1) min
1
0.1min
1
+1

1
]
1
(0.2 0.1) min
1
6.93min
. 8'e reactor volume re9uired is t'e volumetric
low rate divided &0 t'e residence time, ;#$$ gal@min:@6.63 min C #2.23 gal or %.%0 ft
.
.
8'e concentrations o A, ), and C or t'is residence time are

C
A
C
Ao
e
k
1
t
($.# l&mole @ gal: e
0.2min
1
(6.93min)
.025l&mole @ gal

C
B
C
Ao
k
1
(k
1
k
2
)
e
k
2
t
e
k
1
t
[ ]
$.# l&mole @ gal
$.- min
!#
($.- ! $.#:min
!#
e
0.1min
1
(6.93 min:
e
0.2min
1
(6.93 min:
[ ]
$.$+ l&mole @ gal

C
C
k
2
C
Ao
k
1
(k
1
k
2
)
1
k
2
(1e
k2t
)
1
k
1
(1e
k1t
)

1
]
1
C ;$.# min
!#
)(0.1
l&mole
gal
:
$.- min
!#
;$.- ! $.#: min
!#
1
0.1 min
!#
(1 e
0.1min
1
(6.93min)
)
1
0.2 min
!#
(1 e
0.2 min
1
(6.93min)
)

1
]
1
1
1
1
C $.$-+
l&mole
gal
&: I * were not present in large e,cess and actuall0 was a limiting reagent, t'en not as muc' o t'e waste
&0product C would &e ormed &ecause * would not &e present to react wit' product ).

.. Energy Efficient E1traction Cou(led /ith Distillation
Assumption: 8'e low rates o rainate and e,tract p'ases in t'e e,tractor are constant. 8'e ratio o
rainate to e,tract low rate must &e $.7 times t'e minimum ratioW ;R@E: C $.7 ;R@E:
min
. Assume t'at t'e
eed to t'e distillation column is a saturated li9uid. 4se a relu, ratio ;L@1: o #.- times t'e minimum
;L@1:
min
..
a: 1etermine t'e c'ange in re&oiler dut0, Q
R
V , or /
d
values o $.3, $.+, and $.. in t'e e,tractor or
a constant relative volatilit0 in t'e distillation column o
.)S
C 3.
/
d
o $.3,
.)S
C 3.
(irst we must ind t'e slope o t'e operating line t'at makes a <pinc'? wit' t'e e9uili&rium line in t'e
e,traction column. 8'e slope o t'at line is R@E
(in
.
2.
R
E
min
y
x
(K
d
x
o
y
N+1
)
(x
o
x
N
)
(3(.1) .001)
(.1 .01)
0.322
8'e ratio o rainate to e,tract low rate is
R
E
0.8
R
E
min
0.8(0.322) 0.258
and t'e e,tract low rate is

E
R
0.258
# kg @ 'r
0.258
3.88 kg @ 'r
8'e mass raction o our desired component in t'e e,tract leaving t'e column is t'e sum o t'e component
entering t'e column in t'e e,tract stream plus t'at recovered rom t'e rainate stream, assuming constant
low o E ;an assumption:.
y
1
Ey
N+1
+ R(x
o
x
N
)
E
3.88(.001) +1(.1 .01)

3.88
0.024
8'e eed to t'e distillation column is e9ual to t'e e,tract e,iting t'e e,traction column,

F E 3.88 kg @ 'r
and t'e mass raction o t'e distillation column eed is
x
F
y
1
0.024
8'e low rate o t'e distillate can &e o&tained as

D F
(x
F
x
B
)
(x
D
x
B
)
3.88 kg @ 'r
;$.$-2 ! $.$$#:
;$.666 ! $.$$#:
0.091 kg @ 'r
8'e &ottoms product low rate can &e easil0 o&tained.

B F D 3.880.091 kg @ 0r 3.79 kg @ 0r
De must ind t'e <pinc'? point w'ere t'e eed line or t'e distillation column touc'es t'e e9uili&rium
curve or t'e distillation column. 8'is mass raction is
y *
x
F
1 + ( 1)x
F
3 (0.024)
1+ (3 1)0.024
0.069
8'e minimum relu, ratio is
R
Dmin
(x
D
y*)
(y * x
F
)
(0.999 0.069)
(0.069 0.024)
20.439
8'e relu, ration is #.- times t'e minimum.
R
D
1.2 R
Dmin
1.2 (20.439) 24.527
(rom t'e deinition o t'e relu, ratio, we calculate t'e li9uid low rate at t'e top o t'e distillation
column. De assume constant lows in eac' column section or t'is pro&lem.

L R
D
D 24.527(0.091) 2.232 kg @ 0r
8'e vapor low rate at t'e top o t'e column is

V L+ D 2.232+0.091 2.323 kg @ 'r
8'e vapor low rate at t'e &ottom o t'e column is e9ual to t'at at t'e top o t'e column since t'e eed is a
saturated li9uid.

V V 2.323 kg @ 'r
8'e re&oiler dut0 is t'e product o t'e latent 'eat o vaporiJation and t'e vapor low rate at t'e &ottom o
t'e column.

Q
R
V (100 kcal @ kg:;-.3-3 kg @ 'r: 232.3 kg @ 'r
8'ese calculations ma0 &e repeated or eac' value o /
d
o $.+ and $.. and o
",*
C 3 in a similar as'ion.
27
&: 1etermine t'e c'ange in re&oiler dut0 or
.)S
C 3, +, and . in t'e distillation column or a constant
value o /
d
C $.2 in t'e e,tractor.
*imilar to part a: values o t'e re&oiler dut0 are o&tained and are listed in t'e ollowing ta&le as a
summar0.
c: D'ic' parameter, /
d
or
.)S
) 'as t'e greatest inluence on :
R
X
)ot' parameters strongl0 inluence t'e value o :
R
. Increasing /
d
and increasing
.)S
cause a signiicant
decrease in t'e relu, ratio in t'e distillation column, t'ere&0 reducing low rates in t'e column and t'e
re&oiler dut0.
d: Dould 'ig'er or lower values o /
d
or
.)S
result in a more energ0!eicient processX
C'oosing a solvent wit' 'ig' valued or &ot' o t'ese parameters would decrease t'e re&oiler dut0 or t'is
separation.
26
K
d ." .) .* .% .% .%
" " " " ) *
0.322 0.544 0.767 0.433 0.433 0.433
3.879 2.296 1.630 2.885 2.885 2.885
0.024 0.040 0.056 0.032 0.032 0.032
3.879 2.296 1.630 2.885 2.885 2.885
0.024 0.040 0.056 0.032 0.032 0.032
0.091 0.091 0.091 0.091 0.091 0.091
3.788 2.205 1.539 2.794 2.794 2.794
0.069 0.112 0.152 0.091 0.143 0.189
20.439 12.298 8.792 15.357 7.673 5.112
24.527 14.757 10.550 18.429 9.208 6.135
2.232 1.343 0.960 1.677 0.838 0.558
2.323 1.434 1.051 1.768 0.929 0.649
2.323 1.434 1.051 1.768 0.929 0.649
+,al-.r &"&." '%"."! ').'' '*$.# !&.#! $%.!"
R
E
min
E
R
0.8
R
E
min
y
1
Ey
N+1
+ R(x
o
x
N
)
E
F E
1
x
F
y
1
D F
(x
F
x
B
)
(x
D
x
B
)
B F D
y *
x
F
1 + ( 1)x
F
R
Dmin
(x
D
y*)
(y * x
F
)
R
D
1.2 R
Dmin
L R
D
D
V L + D
V V
Q
R
V
InstructorFs note: De ma0 rela, t'e assumption o constant lows in t'e e,traction column and ask t'e
students to perorm parts a: and &: w'ile anal0Jing t'is pro&lem wit' t'e more realistic situation o
var0ing lows o R and E in t'e e,traction column. Ater calculating t'e irst t'ree steps in t'e anal0sis o
part a:, t'e e,iting rainate concentration can &e calculated &0 assuming t'at R does not transer to t'e E
stream. 8'us,
R(1 x
o
) R
N
(1 x
N
)
and solving or R
N
, we o&tain t'e ollowing e9uation.
R
N
R
(1 x
o
)
(1 x
N
)
*imilarl0, rom an e9uation or conservation o solvent in t'e e,tract stream and a component &alance or
t'e column we can calculate t'e e,it e,tract low rate, E
1
, and concentration, y
1
. 8'e remaining
calculations are t'e same. 8'e resulting values are ver0 similar as s'own in t'e ta&le &elow.
+$

0. ,en3ene Emissions from *arious Storage Tan4 Ty(es
+#
K
d ." .) .* .% .% .%
" " " " ) *
0.322 0.544 0.767 0.433 0.433 0.433
3.879 2.296 1.630 2.885 2.885 2.885
0.909 0.909 0.909 0.909 0.909 0.909
0.095 0.093 0.093 0.094 0.094 0.094
3.970 2.387 1.721 2.976 2.976 2.976
0.024 0.039 0.054 0.032 0.032 0.032
3.970 2.387 1.721 2.976 2.976 2.976
0.024 0.039 0.054 0.032 0.032 0.032
0.092 0.092 0.092 0.092 0.092 0.092
3.878 2.295 1.630 2.884 2.884 2.884
0.068 0.109 0.146 0.089 0.140 0.186
20.718 12.661 9.192 15.688 7.839 5.222
24.861 15.193 11.030 18.826 9.407 6.267
2.283 1.395 1.013 1.729 0.864 0.575
2.375 1.487 1.105 1.821 0.956 0.667
2.375 1.487 1.105 1.821 0.956 0.667
+,al-.r &"*.%# '%#.$! ''.%* '#&.) !).)$ $$.*"
R
E
min
E
R
0.8
R
E
min
R
N
R
(1 x
o
)
(1 x
N
)
E
1
y
1
Rx
o
+ Ey
N+1
R
N
x
N
E
1
E(1 y
N+1
) + E
1
y
1
y
1
E
1
y
1
E
1
F E
1
x
F
y
1
D F
(x
F
x
B
)
(x
D
x
B
)
B F D
y*
x
F
1 + ( 1)x
F
R
Dmin
(x
D
y*)
(y * x
F
)
R
D
1.2 R
Dmin
L R
D
D
V L + D
V V
Q
R
V
4sing t'e 8ABE* version 2.$, t'e ollowing results were o&tained using t'e input data provided in t'e
pro&lem statement.
a:
%(R8 = total C #,$26.23 l&@0r, Dorking Losses C 727.2# l&@0r, )reat'ing Losses C #67.$- l&@0r
I(R8 = total C -$7..6 l&@0r, Rim *eal Losses C 36.62 l&@0r, Dit'drawal Losses C 6.2$ l&@0r, 1eck (itting
Losses C #6-..+ l&@0r, 1eck *eam Losses C $.$ l&@0r.
1E(R8 = total C #-2.73 l&@0r, Rim *eal Losses C 36.62 l&@0r, Dit'drawal Losses C 6.2$ l&@0r, 1eck
(itting Losses C .7.7$ l&@0r, 1eck *eam Losses C $.$ l&@0r. Roo 80pe ;pontoon:, 8ank Construction
;welded:
&: "ercent reduction in emissions compared to %(R8
(or I(R8, A C ;%(R8!I(R8:@%(R8,#$$ C ;#,$26.23!-$7..6:@#,$26.23,#$$ C 7$.#A
(or 1E(R8, A C ;%(R8! 1E(R8:@%(R8,#$$ C ;#,$26.23!#-2.73:@#,$26.23,#$$ C 77.#A
c: Comparison to E,ample 6.6!#
8oluene ;l&@0r: )enJene ;l&@0r:
%ertical (i,ed!Roo 8ank 33..6 #,$26.2
Internal (loating!Roo 8ank 66.- -$7.7
1omed E,ternal (loating!Roo 8ank 2-.7 #-2.7
)enJene, &eing more volatile t'an toluene, emits at roug'l0 a actor o t'ree 'ig'er or eac' tank t0pe
compared to toluene. "ercentage reductions are similar or toluene as or &enJene.

2. Storage Tan4 Pollution Prevention +y A((lying -e/ Paint
4sing t'e 8ABE* 2.$ program, t'e ollowing results were o&tained or t'e vertical i,ed!roo storage
tank wit' gra0@medium paint in poor condition or toluene emissions.
a:
/ra0@medium paint in poor condition
%(R8 = total C +$6.-6 l&@0r, Dorking Losses C 32+.+2 l&@0r, )reat'ing Losses C #63..+ l&@0r
8'e percentage o t'e total emissions caused &0 standing ;&reat'ing: losses is 3-.-A.
&: Emissions reduction
Ater t'e application o w'ite paint, t'e annual emissions o toluene are
%(R8 = total C 33..-3 l&@0r, Dorking Losses C -.3.36 l&@0r, )reat'ing Losses C 63.7. l&@0r. 8'is
emission rate is muc' lower ;33.7A: t'an t'e original gra0 paint in poor condition. Kowever, t'ere was
an emission o toluene during t'e painting and paint curing process. 8'is amount o toluene emission is
determined &0 estimating t'e surace area o t'e -$ t!tall ;K: and #- t diameter ;d: tank ; d K C s'ell
area ;.+2 t
-
: G d
-
@2 C dome area!appro,imate ;##3.# t
-
:: and assuming t'at t'e densit0 o t'e paint is 6
l&@gal o paint. Emissions during painting are ;.+2G##3.# t
-
:;# gal paint@#$$ t
-
:;6 l& paint@gal paint:;$.+
l& toluene emitted@l& paint: C -6.$# l& toluene.
+-
8'e net emissions reduction in t'e 0ear o painting t'e tank are +$6.-6 = ;33..-3G-6.$#: C #26.$+ l&@0r.
In t'e second and su&se9uent 0ears, assuming t'at t'e paint remains in good conditions, t'e emissions
reductions are greater, +$6.-6 = 33..-3 C #.-.$6 l&@0r.

+3
Cha(ter '&. !lo/sheet Analysis for Pollution Prevention

'. #eat E1change -et/or4 for Conserving #ot Eater in the #ome
a: Identi0 warm water streams
i. s'ower@&at' tu& ;-: 8 C 3+HC ;6+H(:, F
%ho0e!;tu+
C +67 kg@da0 ;#+$ gal@d:
ii. dis'was'er ;#: 8 C +$HC ;#--H(:, F
di%h0a%he!
C #$$ kg@da0 ;-6 gal@d:
iii. was'ing mac'ine ;#: 8 C 3$HC ;76H(:, F
di%h0a%he!
C -$$ kg@da0 ;+3 gal@d:
&: Annual energ0 savings i warm drain water contact inlet cold water entering 'ot water 'eater.
1ata: 'eat capacit0 o water
.)#
C 2.- k\@;kgLHC:, temperature o entering cold water C #+HC, minimum
temperature driving orce at 'eat e,c'angers C + HC. (inal temperature o 'ot water 'eater water C 6$HC.
*olution: A pinc' diagram suc' as s'own in (igure #$.2 is not needed to solve t'is pro&lem. De simpl0
need to calculate t'e amount o energ0 transerred rom eac' drain stream per da0 and compare t'is to t'e
energ0 needed or eac' use, and t'en convert to an annual &asis. Dit' a +HC minimum temperature
dierence in eac' 'eat e,c'anger, t'e ma,imum temperature to w'ic' t'e cold water can &e 'eated is +HC
less t'an t'e temperature o t'e warm drain water streams.
*'ower@tu& e,c'anger:
Keat e,c'anged
:
%ho0e!;tu+
C
.)#
F
%ho0e!;tu+
T C ;+67 kg@da0:; 2.- k\@;kgLHC::;;3+!+:!#+:HC C 3+,.72 k\@d
Bormal Keat Re9uirement

C
.)#
F
%ho0e!;tu+
T C ;+67 kg@da0:; 2.- k\@;kgLHC::;;6$!#+:HC C #$.,3+- k\@d
"ercent savings on energ0: C 3+,.72 k\@d @ #$.,3+- k\@d ;#$$: C 33.33A
Annual Energ0 *avings: C ;3+,.72 k\@d:;36+ d@0r: C #.3#,#$
.
k\@0r
1is'was'er:
Keat e,c'anged
:
di%h0a%he!
C
.)#
F
di%h0a%he!
T C ;#$$ kg@da0:; 2.- k\@;kgLHC::;; +$!+:!#+:HC C #-,6$$ k\@d

C
.)#
F
di%h0a%he!
T C ;#$$ kg@da0:; 2.- k\@;kgLHC::;;6$!#+:HC C #7,6$$ k\@d
"ercent savings on energ0: C #-,6$$ k\@d @ #7,6$$ k\@d ;#$$: C 66.66A
Annual Energ0 *avings: C ;#-,6$$ k\@d:;36+ d@0r: C 2.6$,#$
6
k\@0r
Das'ing >ac'ine:
Keat e,c'anged
:
0a%h
C
.)#
F
0a%h
T C ;-$$ kg@da0:; 2.- k\@;kgLHC::;; 3$!+:!#+:HC C 7,2$$ k\@d
C
.)#
F
0a%h
T C ;-$$ kg@da0:; 2.- k\@;kgLHC::;;6$!#+:HC C 3.,7$$ k\@d
"ercent savings on energ0: C 7,2$$ k\@d @ 3.,7$$ k\@d ;#$$: C 66.66A
Annual Energ0 *avings: C ;7,2$$ k\@d:;36+ d@0r: C 3.$.,#$
6
k\@0r
+2
Annual *avings on Energ0
Cost o electricit0 C _.$6@kDL'
Eicienc0 o electric 'ot water 'eater C +$A ;including 'eat losses rom t'e tank:
Conversion actorW # kDL' C 3,6$$.6 k\
8otal energ0 savings C ;#.3#,#$
.
G 2.6$,#$
6
G 3.$.,#$
6
:k\@0r @ $.+ C 2.#+ ,#$
.
k\@0r
Annual savings on energ0 C ;2.#+ ,#$
.
k\@0r:; # kDL'@3,6$$.6 k\:; _.$6@kDL': C _66-
c: Calculate time re9uired to recover installation costs rom savings
Cost per e,c'anger C _+$$
Bum&er o e,c'angers needed C 2
8otal cost o installing e,c'angers C ;2:;_+$$: C _-,$$$
8ime needed to recover installation costs or e,c'angers C _-,$$$@;_66-@0r: C -.6 0rs

%. Pinch Point Determination for a Mass E1changer -et/or4
*tream Inormation
/i,. 0tream 1lo2 /ate (+g-s) yin yout 34uilibrium
+1 3 0.45 0.1 y ! 0.5 '
0.8
+2 3 0.3 0.1 y ! 1.5 '
5ean 0tream 1lo2 /ate (+g-s) xin xout
,1 5 0.1 0.45
>ass (raction Conversion 8a&le
/i,. 0tream 1lo2 /ate (+g-s) xin6 xout6
+1 3 0.8766 0.13375
+2 3 0.2 0.06667
5ean 0tream 1lo2 /ate (+g-s) xin xout
,1 5 0.1 0.45
>ass E,c'ange *ummar0 8a&le
7ass Cummulative
/i,. 0treams 3x,.anged 7ass
x6 Interval (+g-s) Comments (+g-s)
.877 to .2 -0.936 y ! .45 to .138 .or %tr/a0 +1 -0.936
.2 to .13375 -0.414 y ! .138 to .1 .or %tr/a0 +1 and y ! .3 to .2 .or +2 -1.35
.13375 to .06667 -0.3 y ! .2 to .1 .or %tr/a0 +2 -1.65
,1 %tr/a0 1.75 .or '* .ro0 .1 to .45
A plot o t'e composite load line diagram is s'own in t'e ne,t igure, w'ere t'e mass e,c'anged or t'e
ric' streams is negative, indicating mass loss rom t'e ric' stream, and is positive or t'e lean stream,
indicating mass gain &0 t'is stream.
++
In order to create t'e pinc' on t'e com&ined load line diagram, we must amovea t'e ric' composite curve
verticall0 until it touc'es t'e lean curve. 8'e pinc' will occur at a mass raction o $.-, w'ere t'e value
o t'e mass e,c'anged on t'e lean curve is $.+ kg@s. 8'ereore, we need to add t'e dierence &etween t'e
two curves at , C $.- to eac' point on t'e ric' composite load line curve ;$.+ !;!.636: C #.236. 8'e
com&ined load line diagram wit' t'e pinc' is s'own on t'e ne,t igure.
E,tra Credit: (rom t'e diagram &elow, we can calculate t'e percentage o mass transer rom t'e ric' and
lean streams t'at can &e accomplis'ed &0 t'e internal mass e,c'ange network versus t'e percentage o
mass transer t'at must &e accomplis'ed using e,ternal mass separating agents. 8'e internal network o
mass e,c'angers is a&le to transer at a rate o #.236 kg@s. 8'is represents #.236@#..+U;#$$: C 7-.#A o
t'e load o t'e lean stream and #.236@#.6+U;#$$: C 7..$A o t'e load o t'e ric' streams. An e,ternal
mass separating agent will &e re9uired to increase t'e mass raction o t'e lean stream rom $.363 to $.2+
wit' a mass loading o #..+!#.236C.3-2 kg@s. *imilarl0, or ric' stream -, an e,ternal mass separating
agent will &e re9uired to remove $.-#2 kg@s rom t'is stream in order to reduce its concentration rom ,U
C $.##2 to ,U C .$666..
+6
Combined 5oad 5ine 8iagram
-2
-1.5
-1
-0.5
0
0.5
1
1.5
2
0 0.2 0.4 0.6 0.8 1
x( mass fra,tion (5ean)
7
a
s
s

3
x
,
.
a
n
g
e
d

(
+
g
-
s
)
+ich Co0posit/ C1r2/ ,/an C1r2/

.. Styrene Process: Mass E1change -et/or4 Pinch Analysis
*t0rene
(ormula: C7K7
>olecular Deig't: #$2.#+
CA* Registr0 Bum&er: #$$!2-!+

*tream Inormation
/i,. 0tream 1lo2 /ate (+g-.r) yin yout 34uilibrium
+1 to stripp/r 70*607 1.77'10
-3
1.5'10
-4
y ! 0.001 '
+2 to adsorb/r 70*607 1.5'10
-4
5.7'10
-6
y ! 0.00071 '
5ean 0tream 1lo2 /ate (+g-.r) xin xout
,1 to stripp/r 70 0.0 1.62 y ! 0.001 '
,2 to adsorb/r 53 3'10
-5
0.2 y ! 0.00071 '
+.
Composite 5oad 5ine 8iagram 2- Pin,.
-0.5
0
0.5
1
1.5
2
0 0.2 0.4 0.6 0.8 1
x( mass fra,tion (5ean)
7
a
s
s

3
x
,
.
a
n
g
e
d

(
+
g
-
s
)
a: Composition Interval 1iagram or Ric' *treams
&: Composition Interval 1iagram or Lean *treams
+7
#...,#$
!3
#.+,#$
!2
+,#$
!6
0 scale
Interval M#
Interval M-
Ric' *treams
M# M-
#.6-
.-$$
3,#$
!+
, scale
Interval M#
Interval M-
Lean *treams
M# M-
Interval M3
$
c: "inc' 1iagram
In t'is pro&lem, &ecause t'e ric' streams are &ot' a9ueous &ased and t'ereore similar, we will convert
t'e lean stream mass ractions to a ric' mass raction &asis using t'e e9uili&rium relations'ips.
/i,. 0tream 1lo2 /ate (+g-.) yin yout
+1 70607 0.00177 0.00015
+2 70607 0.00015 0.0000057
5ean 0treams 1lo2 /ate (+g-.) y6in y6out
,1 to stripp/r 70 0 0.00162
,2 to adsorb/r 53
2.13'10
-8
0.000142
A plot o t'e composite load line diagram is s'own in t'e ne,t igure, w'ere t'e mass e,c'anged or t'e
ric' streams is negative, indicating mass loss rom t'e ric' stream, and is positive or t'e lean stream,
indicating mass gain &0 t'is stream.
+6
7ass Cummulative
y Interval (+g-.) Comments (+g-.)
.00177 to .00015 -114.38334 y ! .00177 to .00015 .or %tr/a0 +1 -114.38334
.00015 to .0000057 -10.18859 y ! .00015 to .0000057 .or %tr/a0 +2 -124.57193
5ean 0treams (+g-.) Comments
0 to 2.13'10
-8
0.001491 .or '* .ro0 0 to 2.13'10
-5
.or ,1 0.001491
2 .13'10
-8
to .000142 20.537 .or '* 2.13'10
-5
to .142 .or ,1 3 3'10
-5
to .2 .or ,2 20.538
.000142 to .00162 103.460 .or '* .ro0 .1423 to 1.62 .or ,1 123.998
In order to create t'e pinc' on t'e com&ined load line diagram, we must amovea t'e ric' composite curve
verticall0 until it touc'es t'e lean curve. 8'e pinc' will occur at a mass raction o $.$$$$$+., w'ere t'e
value o t'e mass e,c'anged on t'e lean curve is $.7- kg@s. 8'ereore, we need to add t'e dierence
&etween t'e two curves at , C $. $$$$$+. to eac' point on t'e ric' composite load line curve ;$.7- !;!
#-2.+.: C #-+.36 kg@'. 8'e com&ined load line diagram wit' t'e pinc' is s'own on t'e ne,t igure.
6$
Composite 5oad 5ine 8iagram 2- Pin,.
0
20
40
60
80
100
120
140
0 0.0005 0.001 0.0015 0.002
y( mass fra,tion (/i,. Basis)
Combined 5oad 5ine 8iagram
-150
-100
-50
0
50
100
150
0 0.0005 0.001 0.0015 0.002
)a'i010
B/n4/n/
5'chan6/ !
123.18 763hr
8'e rate o &enJene mass e,c'ange can &e calculated rom t'e pinc' diagram &0 taking t'e dierence
&etween t'e ma,imum value o mass e,c'anged on t'e lean curve ;#-3.667 kg@': and su&tract t'e
minimum value o mass e,c'anged on t'e ric' curve at pinc' ;$.7- kg@':, as s'own on t'e igure a&ove.
8'e value o t'e &enJene recovered is ;_$.- @ kg &enJene: ;#-3.#7 kg &enJene@'r: C _-2.62 @ 'r.
(or t'e case o a minimum mass transer driving orce o $.$$#, we must move t'e ric' composite curve
down until t'e 'oriJontal distance on t'e pinc' diagram &etween t'e lean and ric' curves is $.$$#, w'ic'
is at t'e pinc' point in t'e composite load line diagram w@pinc', a&ove. 8'e 'oriJontal distance o $.$$#
mass raction units is measured rom t'e terminus o t'e lean composite curve at coordinates ;0C-.#3,#$
!
7
, >ass E,c'angedC$.$$#26#:. 8o determine t'e vertical distance, we must multipl0 t'e 'oriJontal
distance ;$.$$#G-.#3,#$
!7
: &0 t'e slope o t'e ric' composite curve ;.$,6$. kg@': w'ic' is e9ual to .$.6#
kg@'. 8'e modiied diagram is s'own &elow.
8'e ma,imum rate o &enJene transer w'en t'e minimum driving orce is $.$$# can &e o&tained rom t'e
igure a&ove, ;+2..7!$.$$#26#: kg@' C +2..7 kg@'.
8'e value o t'e &enJene recovered is ;_$.- @ kg &enJene: ;+2..7 kg &enJene@'r: C _#$.66 @ 'r.
e: 8'e recover0 rate o &enJene rom t'e steam stripper calculated using t'e anal0sis in part c is #-3.#7 kg
&enJene@'r and t'is compares wit' ##3 kg@'r recovered rom t'e decanter plus ## kg@'r recovered rom
t'e decanter downstream rom t'e regenerator o t'e adsorption regenerator unit or a total o #-2 kg@'r.
8'e agreement is ver0 close.
6#
Composite 5oad 5ine 8iagram 2- 9 .'
-100
-50
0
50
100
150
0 0.0005 0.001 0.0015 0.002
7
a
s
s

3
x
,
.
a
n
g
e
d

(
+
g
-
.
)
+ich Co0posit/ C1r2/ ,/an Co0posit/ C1r2/

0. Co((er Etching from Circuit ,oards
/i,. 0tream 1lo2 /ate (+g-s) yin yout 34uilibrium
+1 0.25 0.13 0.10
+2 0.02 0.06 0.02
5ean 0treams 1lo2 /ate (+g-s) 7ax :( 7ax y6in :( y6out
%1 88 0.07 0.053 0.03 0.0233 y ! 0.734 '90.001
%2 88 0.20 0.40 0.001 0.1015 y ! 1.5 '90.1
a: Composition Interval 1iagram or Ric' and Lean *treams
Composition Interval 1iagram or Lean *treams
6-
$.#3
$.#$
$.$-
0 scale
Interval M#
Interval M-
Ric' *treams
M# M-
$.$6
&: >a,imum amount o copper removed using *#
7ass Cummulative
y Interval (+g-s) Comments (+g-s)
0.13 to 0.1 -0.0075 -0.0075
0.06 to 0.02 -0.0008 -0.0083
8'e plot o t'e load line diagram or t'e ric' streams is s'own in t'e ne,t igure. 8'e lean curve or *# is
missing &ecause t'e low rate is not speciied, and s'ould &e calculated as part o t'e solution. De can
move t'e ric' curve up until it touc'es t'e lean curve, w'ic' terminates at t'e point on t'e diagram
;$.$-33, $ kg@s:. In order to do t'is, we add t'e vertical dierence &etween t'e two curves at t'is pinc'
point ;$.$$73 kg@s: to eac' point on t'e ric' curve. 8'e ot'er end o t'e lean curve or stream *# must
terminate at t'e point on t'e diagram ;$.$+3, .$$7-3 kg@s: so t'at t'e ma,imum copper concentration or
stream *# is not e,ceeded w'ile using t'e minimum possi&le low rate o *#.
63
$.2$
$.#$#+
$.$+3
0U scale
Interval M#
Lean *treams
M# M-
Interval M-
$.$-33
8'e com&ined load line diagram wit' pinc' is s'own in t'e ne,t igure. 8'e pinc' occurs at t'e &ottom
o t'e lean curve.
62
Combined 5oad 5ine 8iagram( 0
'
-0.009
-0.008
-0.007
-0.006
-0.005
-0.004
-0.003
-0.002
-0.001
0
0 0.02 0.04 0.06 0.08 0.1 0.12 0.14
7
a
s
s

3
x
,
.
a
n
g
e
d

(
+
g
-
s
)
+ich Co0posit/ C1r2/
Composite 5oad 5ine 8iagram 2- Pin,.( 0
'
-0.001
0
0.001
0.002
0.003
0.004
0.005
0.006
0.007
0.008
0.009
0 0.02 0.04 0.06 0.08 0.1 0.12 0.14
7
a
s
s

3
x
,
.
a
n
g
e
d

(
+
g
-
s
)
8'e re9uired low rate o stream *
#
is o&tained rom t'e ma,imum rate o copper mass e,c'ange ;$.$$7-3
kg@s: and t'e actual mass raction values o t'e inlet ;,C.$3: and outlet stream ;,C.$.:, e9ual to ;$.$$7-3
kg@s:@;.$.!.$3: C $.-$6 kg@s.
c: >a,imum amount o copper removed using *-
8'e plot o t'e load line diagram or t'e ric' streams is again t'e igure irst igure in part &. 8'e lean
curve or *- is missing &ecause t'e low rate is not speciied, and s'ould &e calculated as part o t'e
solution. De can move t'e ric' curve up until it touc'es t'e lean curve, w'ic' terminates at t'e point on
t'e diagram ;$.#$#+, $ kg@s:. In order to do t'is, we add t'e dierence &etween t'e two curves at t'is
pinc' point ;$.$$.-$ kg@s: to eac' point on t'e ric' curve. 8'e ot'er end o t'e lean curve or stream *-
must terminate at t'e point on t'e diagram ;$.#3, .$$.-$ kg@s: so t'at t'e ma,imum copper concentration
or stream *- does not violate e9uili&rium constraints w'ile using t'e minimum possi&le low rate o *-.
8'e com&ined load line diagram wit' pinc' or stream *- is s'own in t'e ne,t igure. )ot' composite
curves la0 on top o eac' ot'er. 8'e re9uired low rate o stream *- is o&tained rom t'e ma,imum rate
o copper mass e,c'ange ;$.$$.-$ kg@s: and t'e actual mass raction values o t'e inlet ;,C.$$#: and
outlet stream ;,C.$-:, e9ual to ;$.$$.-$ kg@s:@;.$-!.$$#: C $.$36- kg@s.
d: 8'e ma,imum amount o copper t'at can &e recovered using &ot' *# and *- is t'e greater o t'e
amounts calculated in parts & and c, $.$$7-3 kg Copper@s.
6+
Composite 5oad 5ine 8iagram 2- Pin,.( 0
&
-0.002
-0.001
0
0.001
0.002
0.003
0.004
0.005
0.006
0.007
0.008
0 0.02 0.04 0.06 0.08 0.1 0.12 0.14
7
a
s
s

3
x
,
.
a
n
g
e
d

(
+
g
-
s
)
+ich Co0posit/ C1r2/ ,/an Co0posit/ C1r2/
e: I t'e cost o *- is #@- t'e cost o *#, determine t'e optimum ratio o t'e streams t'at still recovers t'e
ma,imum amount o copper.
*tream *# must recover copper over t'e ric' stream range o $.$-3-6O0O$.#$#+ &ecause *- can not recover
copper in t'at range due to e9uili&rium constraints. 8'e low rate o *# over t'is range o 0 is e9ual to t'e
rate o copper e,c'anged ;.$$## kg copper@s: divided &0 t'e mass raction c'ange ;.#$#+!.$-:, w'ic' gives
$.$#3+ kg *#@s. Also, over t'e range o $.#$#+O0O$.#3, stream *- s'ould &e used &ecause it is t'e c'eapest
and its low rate or eac' unit o copper recovered is muc' less t'an *#. 8'ereore, t'e optimum ratio *#@*-
C ;$.$#3+ kg *#@s:@; $.$36- kg *- @s: C $.3..

2. Source7Sin4 Diagrams for )m(roved )ndustrial Eater Dse
*ink *treams
:lo; +at/ )a'i010
%tr/a0s 10
3
763hr Conc. "pp0$
1 50 20
2 100 50
3 80 100
4 70 200
*ource *treams
:lo; +at/ )a'i010
%tr/a0s 10
3
763hr Conc. "pp0$
A 50 50
B 100 100
C 70 150
< 60 250
8'e source!sink diagram or t'is network o streams is s'own in t'e ne,t igure. In general, t'e source
concentrations are 'ig'er t'an t'e sink concentrations, &ut one source 'as t'e target concentration o a
sink &ut a 'ig'er low rate ;) and 3: w'ile anot'er source 'as t'e target low rate o a sink &ut a lower
concentration ;C and 2:. 8'e latter source can &e used to satis0 its sink &ecause t'e concentration targets
are ma,imum onl0 and a lower concentration can &e tolerated. A portion o source ) ;7$,$$$ kg@': can
&e used to satis0 sink 3.
66
Dit' t'ese matc'es made, a new source!sink diagram can represent t'e remaining streams. 8'e
remaining -$,$$$ kg@' o source stream ) is indicated wit' a prime in t'e diagram.
6.
0our,e;0in+ 8iagram
0
20
40
60
80
100
120
0 50 100 150 200 250 300
Contaminant Con,entration (ppm)
7
a
s
s

1
l
o
2

/
a
t
e

(
'

+
g
-
.
r
)
%in7s %o1rc/s
1
2
3
4
A
B
C
<
7odified 0our,e;0in+ 8iagram
0
20
40
60
80
100
120
0 50 100 150 200 250 300
Contaminant Con,entration (ppm)
1
l
o
2

/
a
t
e

(
+
g
-
.
)
%in7s %o1rc/s
1
2
A
B=
<
*ource streams A and )F plus 3$,$$$ kg@' o pure water can &e com&ined to satis0 t'e low rate
re9uirements o sink -. 8'e concentration o t'is com&ined source is

C
;+$,$$$ kg @ ':;+$ ppm: G ;-$, $$$ kg @ ':;#$$ ppm: G ;3$, $$$ kg @ 'r:;$ ppm:
;+$, $$$ G -$, $$$ G 3$, $$$: kg @ '
C 2+ ppm
w'ic' is less t'an t'e ma,imum allowa&le concentration o t'e sink stream ;+$ ppm:. Bow all o t'e
source streams 'ave &een ull0 utiliJed e,cept or 1, w'ic' will 'ave to &e treated and disposed o. As
or sink #, t'is could &e satisied wit' pure water at a low rate o +$,$$$ kg@'.
8'e total res' water demand o t'is mass e,c'ange network is 7$,$$$ kg@' and t'e total low rate o
source wastewater needing treatment is 6$,$$$ kg@' at a concentration o -+$ ppm.
8'is solution is ver0 similar to t'e network arrived at &0 "olle0 and "olle0, C'emical Engineering
"rogress, (e&. -$$$, (igures 7 and 6.

67
Cha(ter ''. Evaluating the Environmental Performance of a !lo/sheet

'. Ma1imum )ncremental Reactivity of Reformulated !uel ,lends
1ata: c'emical >IR
et'anol #.32
toluene -..$
,0lene ..#$
&ase uel #.+
#$A et'anol, 6$A &ase uel "ercent Reduction
>i,ture >IR C ;.#:;#.32:G;.6:;#.+: C #.27
#$A toluene, 6$A &ase uel
>i,ture >IR C ;.#:;-..:G;.6:;#.+: C #.6- ;#.27!#.6-:@#.6-;#$$:C !7.6A
#$A ,0lene, 6$A &ase uel
>i,ture >IR C ;.#:;..#:G;.6:;#.+: C -.$6 ;#.27!-.$6:@-.$6;#$$:C !-7.-A

%. #ydro1yl Radical Reaction /ith Ethene
1ata: k C -nd !order rate constant or reaction o et'ene wit' 5KL C -..,#$
!#3
;cm
3
@;molec.Lsec::
S5KLT C #$
!#-
moles @ L
a: pseudo!#st!order reaction rate constant ;kS5KLT:
S5KLT C ;#$
!#-
moles@L:;6.$-,#$
-3
molecules@mole:;# L@#$$$ cm
3
: C 6.$-,#$
7
molecules@cm
3
kS5KLT C ;-..,#$
!#3
;cm
3
@;moleculesLsec:::;6.$-,#$
7
molecules@ cm
3
: C #.63,#$
!2
sec
!#
C $.+6 'r
!#
&: Et'ene remaining ater # 'our
Initial concentration o et'ene is #$$ ppm.
(rom C'apter +, SEt'eneT C SEt'eneT
o
e,p;!kS5KLTt:
C ;#$$ ppm: e,p;!;.+6 'r
!#
:;# 'r:: C ++.. ppm

.. Glo+al Earming Parameters
a: 8'e c'emicals in 8a&le 1!# 'aving t'e 'ig'est values o &ot' and )I can &e ound &0 taking t'e
product o t'ese two parameters or eac' c'emical and t'en ranking t'e c'emicals in descending order.
8'e igure &elow s'ows an increasing trend in /D" wit' t'e product L)I, indicating t'e importance o
t'ese two parameters on /D".
66
C'emical (ormula ;0rs: )I ;atm
!#
cm
!-
: L)I /D"

C(C!##+ C(3CCl(- 2$$.$ 26.7 #,7.#,-$$ .$$$
C(C!##2 CCl(-CCl(- -$$.$ 2#2# 7-7,-$$ .$$$
C(C!#- CCl-(- #-$.$ 3-2$ 377,7$$ .#$$
C(C!##3 CCl-(CCl(- 6$.$ 32$# 3$6,$6$ 2+$$
C(C!## CCl3( 6$.$ -376 #23,32$ 32$$
KC(C!#2-& C-(-K3Cl #6.# -+.. +6,--# #7$$
8etrac'loromet'ane CCl2 2..$ ##6+ +6,#6+ #3$$
KC(C!-- C(-KCl #+.$ -++2 37,3#$ #6$$
KC(C!#-2 C-(2KCl 6.6 2$23 -.,76. 22$
KC(C!#2#& C-(K3Cl- #$.7 #.3- #7,.$6 +7$
#,#,#!tric'loroet'ane CK3CCl3 6.# #-$6 .,3.+ #$$
KC(C!#-3 C-(3KCl- #.. -++- 2,337 6$
1ic'loromet'ane CK-Cl- $.+ #6$2 7$- 6
&: De ma0 estimate t'e magnitude o eac' partial derivative in t'e ollowing e9uation
d(GWP) = (
GWP
)
BI
d + (
GWP
BI
)
dBI
&0 inspection o t'e /D" ta&le and a simple dierence calculation.
.$
1
10
100
1000
10000
100 1*000 10*000 100*000 1*000*000 10*000*000
<BI

;
/D"
:
)I
is estimated &0 using c'emicals wit' nearl0 t'e same value o )I &ut dierent values o .
8'e ollowing two c'emicals will work.
C'emical (ormula ;0rs: )I ;atm
!#
cm
!-
: L)I /D"

KC(C!#2-& C-(-K3Cl #6.# -+.. +6,--# #7$$
KC(C!-- C(-KCl #+.$ -++2 37,3#$ #6$$

;
/D"
:
)I

#7$$ !#6$$
#6.#!#+.$
C 27.7 0r
!#
. De ma0 wis' to consider two c'emicals more widel0 separated
in terms o , or e,ample C(C!#- and KC(C!##3.

;
/D"
:
)I

.#$$ ! 2+$$
#-$ ! 6$
C 76.. 0r
!#
. (inall0, using tetrac'loromet'ane and #,#,#!tric'loroet'ane

;
/D"
:
)I

#3$$ !#$$
2. ! 6.#
C -6.3 0r
!#
. De mig't use an average o t'ese or a representative num&er,
++ 0r
!#
.
(or t'e term

;
/D"
)I
:
, our c'oices rom t'e ta&le a&ove are limited. De c'oose KC(C!#-2 and #,#,#!
tric'loroet'ane or t'is calculation.

;
/D"
)I
:

22$ !#$$
2$23 !#-$6
C $.#- ;atmL cm
-
).
c:

d;/D": C ;
/D"
:
)I
L d G ;
/D"
)I
:
L d)I
C ;++ 0r
!#
);#$ 0r: G ;.#- atmL cm
-
);2$$ atm
!#
L cm
!-
)
C ++$ G 27 C +67
8'e residence time in t'e atmosp'ere, , appears to 'ave t'e dominant eect on /D".

0. )ncremental Reactivities for *olatile rganic Com(ounds
a: Average >IRs or compound classes: I we place t'e average >IR or compound classes in descending
order and include t'e average >IR or reactive organic gases ;R5/:, t'e ollowing list is o&tained.
Alde'0des, compounds wit' car&on!car&on dou&le &onds, and aromatics are more potent smog orming
c'emicals ;low level atmosp'eric oJone ormation:.
o(pound la%% <IR
alde'0des ..-2
ot'er alkenes 6.7+
secondar0 alkenes 6..+
primar0 alkenes +.66
.#
aromatics 2.32
+ase reactive organic gas mi1ture ..'&
acet0lenes -.3$
c0clic alkanes -.$6
alco'ols and et'ers #.3-
&ranc'ed alkanes #.-$
aromatic o,0genates $.6+
ketones $.7.
n!alkanes $.++
&: I one o t'e main considerations or c'oosing a compound or a reormulated gasoline is smog
ormation potential, t'e compounds to consider would &e in t'e compound classes o alco'ols and et'ers,
aromatic o,0genates, and ketones since t'e0 all 'ave >IR values &elow t'e &ase R5/ mi,ture. All o
t'ese classes 'ave o,0gen atoms integrated into t'e molecule and t'e presence o t'e o,0gen will
decrease C5 emissions.

2. Environmental inde1 calculations for the case study of toluene and ethyl acetate recovery and
recycle from E1am(le ''..7%.
8'e emissions or t'e a&sor&er oil low rates o $ and #$$ kgmole@min are given &elow. n!C#2 is t'e
a&sor&er oil and 'e,ane will &e used or 85C, a &0product o utilit0 &oiler com&ustion.
A+sor+er
il !lo/
Rate
;kgmol@'r:
Emission Rate ;kg@'r:
Toluene
Ethyl
Acetate C
%
C TC -1 S1 n7C'0
$ #63.++ #63.++ $ $.$ $.$ $.$ $.$ $.$
#$$ $.$- #-7.$. 36$ $.#-6 $.$$. $.+- 3.36 2.-3
A+sor+er il !lo/ Rate @ & 4gmole?hr
/lo&al warming inde,: I
=#
;=#.
i
(
i
:
i
8'e glo&al warming potential or eac' emitted c'emical must &e calculated using e9uation ##.3!+,
=#.
i
;indi!ect : N
<#
O
-
<#
i
.
(or toluene, =#.
i
;indirect: C ;. car&ons:;22@6-: C 3.3+ and
or et'0l acetate, =#.
i
;indirect: C ;2 car&ons:;22@77: C -.$
I
=#
C ;3.3+:;#63.+ kg@'r: G ;-:;#63.+ kg@'r: C #,$3+ kg@'r
*mog (ormation Inde,: I
SF
;SF.
i
(
i
:
i
8'e ma,imum incremental reactivit0 or a c'emical is provide in Appendi, 1, 8a&le 1!2.

.-
8'e smog ormation potential or a c'emical is
SF.
i
<IR
i
<IR
RO=
(or toluene, SF.
i
C -..@3.#C$.7. and or et'0l acetate, SF.
i
C #.#@3.#C$.3+ ;an average o alco'ols and
et'ers and ketones:.
I
SF
C ;$.7.:;#63.+ kg@'r: G ;$.3+:;#63.+ kg@'r: C -3. kg@'r
Acid Rain Inde,: I
AR
C $, 8'ere are no acid orming c'emicals emitted or t'is case.
5Jone 1epletion Inde,: 8'ere are no oJone depleting c'emicals emitted or t'is case.
Bon!Carcinogenic Ingestion 8o,icit0 Inde,: I
IN=
;IN=T.
i
(
i
:
i
8'e ingestion to,icit0 potential is given &0 e9n. ##.3!#2

INGTP
i
(C
i, w
) / (RfD
i
)
(C
Toluene, w
) / (RfD
Toluene
)
or
INGTP
i
(C
i, w
) / (LD
50,i
)
(C
Toluene, w
) / (LD
50,Toluene
)
depending upon t'e availa&ilit0 o data.
(or toluene, data is given in E,ample ##.3!3W IN=T.
i
C S;2.$,#$
!.
g@m
3
:@;$.- mg@kg@da0:T @ S;2.$,#$
!.

g@m
3
:@;$.- mg@kg@da0:T C #.$.
(or et'0l acetate, IN=T.
i
C S;+.$,#$
!6
g@m
3
:@;$.6 mg@kg@da0:T @ S;2.$,#$
!.
g@m
3
:@;$.- mg@kg@da0:T C -.7.
I
IN=
C ;#.$:;#63.+ kg@'r: G ;-.7:;#63.+ kg@'r: C .3+ kg@'r.
Bon!Carcinogenic In'alation 8o,icit0 Inde,: I
INH
;INHT.
i
(
i
:
i
8'e ingestion to,icit0 potential is given &0 e9n. ##.3!#2

INHT.
i
i, a
@ Rf
i
Toluene, a
@ Rf
Toluene
or
INGTP
i
(C
i, a
) / (LC
50,i
)
(C
Toluene, a
) / (LC
50,Toluene
)
depending upon t'e availa&ilit0 o data.
(or toluene, data is given in E,ample ##.3!3W INHT.
i
C S;#.6.,#$
!.
g@m
3
:@;2,$$$ ppm:T @ S;#.6.,#$
!.

g@m
3
:@;2,$$$ ppm:T C #.$.
(or et'0l acetate, INHT.
i
C S;2.36,#$
!.
g@m
3
:@;3-$$ ppm:T @ S;#.6.,#$
!.
g@m
3
:@;2,$$$ ppm:T C -.7.
I
INH
C ;#.$:;#63.+ kg@'r: G ;-.7:;#63.+ kg@'r: C .3+ kg@'r.
A+sor+er il !lo/ Rate @ '&& 4gmole?hr
/lo&al warming inde,: I
=#
;=#.
i
(
i
:
i
I
=#
C ;3.3+:;$.$- kg@'r: G ;-:;#-7.$. kg@'r: G ;#.$:;36$ kg@'r: C 6#6 kg@'r
*mog (ormation Inde,:
(or n!C#2, SF.
i
C $.3-@3.#C$.#$ and or 85C ;'e,ane:, SF.
i
C $.67@3.#C$.3-.
I
SF
C ;$.7.:;$.$- kg@'r: G ;$.3+:;#-7.$. kg@'r: G ;$.#$:;2.-3: G ;$.67:;$.$$.: C 2- kg@'r
.3
Acid Rain Inde,: I
AR
;AR.
i
(
i
:
i
8'e acid rain potentials or a c'emical,

AR.
i
SO-
, are given in 8a&le 1!3 in Appendi, 1.
(or *5,, AR.
i
C #.$ ;assuming *5-:, and or B5,, AR.
i
C #.$. ;assuming B5:.
I
AR
C ;#.$:;3.36 kg@'r: G ;#.$.:;$.+- kg@'r: C 2.$ kg@'r
Bon!Carcinogenic Ingestion 8o,icit0 Inde,:
(or 'e,ane, data is given in E,ample ##.3!3W IN=T.
i
C S;#.+,#$
!6
g@m
3
:@;-7,.$$ mg@kg:T @ S;2.$,#$
!.

g@m
3
:@;+,$$$ mg@kg:T C 6.+,#$
!2
.
I
IN=
C ;#.$:;$.$- kg@'r: G ;-.7:;#-7.$. kg@'r: G ;6.+,#$
!2
:;$.$$.: C 3+6 kg@'r.
Bon!Carcinogenic In'alation 8o,icit0 Inde,:
(or 'e,ane, data is given in E,ample ##.3!3W INHT.
i
C S;#.6.,#$
!.
g@m
3
:@;$.- mg@m
3
:T @ S;#.6.,#$
!.
g@m
3
:@
; $.2 mg@m
3
:T C -.$.
I
INH
C ;#.$:;$.$- kg@'r: G ;-.7:;#-7.$. kg@'r: G ;-.$:;$.$$.: C 3+6 kg@'r.

5. Car+on Dio1ide Emission !actors
Fuel Oil: assume stoichiometry of C
#$
K
--
G #+ #@- 5
-
#$ C5
-
G ## K
-
5
)asis o # mole C
#$
K
--

>oles o C5
-
C #$ moles
>ass o C5
-
C ;#$ moles:;22 g@mole: C 22$ g C5
-
C $.22 kg C5
-
%olume C
#$
K
--
C ;# mole C
#$
K
--
:;#22 g@mole:;# kg@#$
3
g:@;$..3 kg@L: C $.#6. L C
#$
K
--
C5
-
emission actor C $.22 kg C5
-
@ $.#6. L C
#$
K
--
C -.-3 kg C5
-
@ L C -,3$$ kg C5
-
@#$
3
L.
I a speciic gravit0 o uel oil closer to # is c'osen, t'en t'e emission actor is ver0 close to t'e value
given in 8a&le 7.3!+ o 3,$-+ kg@#$
3
L.
Natural Gas: assume stoichiometry of CK
2
G - 5
-
C5
-
G - K
-
5
)asis o # mole CK
2

>oles o C5
-
C # mole
>ass o C5
-
C ;# moles:;22 g@mole: C 22 g C5
-
C $.$22 kg C5
-
%olume CK
2
at standard conditions C ;# mole CK
2
:;--.2 L@mole:;#$
!3
m
3
@L: C
C5
-
emission actor C $.$22 kg C5
-
@ $.$--2 m
3
CK
2
C #.66 kg C5
-
@ m
3
CK
2
C #.66,#$
6
kg C5
-
@ #$
6
m
3
CK
2
.
8'e value o emission actor or C5
-
on 8a&le 7.3!6 is #.6.,#$
6
kg C5
-
@ #$
6
m
3
CK
2
.
.2
Cha(ter '%. Environmental Cost Accounting

'. Estimating Tier ' 9#idden: Environmental Costs for Cyclohe1anone?Cyclohe1anol Production
Costs: c0clo'e,anone ;_$..3@l&:, c0clo'e,anol ;_$.73@l&:, rom c0clo'e,ane ;_$.#66@l&:
Ra0 <ate!ial% pe! (ole of cyclohexanone;cyclohexanol A&-6 <olecula! 0ei-ht (<#) > 99
#.# mole c0clo'e,ane ;>DC 72:
- moles o,0gen ;derived rom air ! no material ac9uisition cost:
#a%te% -ene!ated pe! pound of p!oduct
$.$6$ pounds o organics in t'e gaseous eluent to &e treated
$.- pounds o organic a9ueous wastes to sent to water treatment
Raw materials costs per pound o product are:
;#.# l&mole:;72 l& c0clo'e,ane@l&mole:;_ $.#66@l& c0clo'e,ane: C _#+.32 per 66 l& product
C F&.'22 ?l+ (roduct
>ass &alance on gaseous eluent is:
Assuming complete utiliJation o t'e o,0gen in t'e inlet air stream, t'e gaseous waste stream will contain
B
-
in t'e 9uantit0,
;# mole B
-
@$.- moles 5
-
:;- moles 5
-
consumed: per mole product C #$ moles B
-
@mole product.
C ;#$:;-7:@66
C -.73 l& B
-
@l& product
8'e total gaseous waste stream mass is -.73 G $.$6 C -.76 l& gaseous waste @ l& product.
Daste treatment operating costs per pound o product are:
;-.76 l& gas@l& product:;#.+,#$
!2
_@l& gas:G;$.- l& water@l& product:;..2,#$
!+
_@l&water: C 0.0<1'&
70
F?l+
(roduct.
Daste treatment operating costs are ;2.27,#$
!2
@$.#++: ;#$$: C $.3A o raw material costs.

%. Select a (rocess documented in the AP70% documents at ///.e(a.gov?chief? and estimate the
costs of /aste treatment (er (ound of (roduct.
C'apter + *ection # o t'e A"!2- documents on t'e AirC'ie 7.$ C1 contains a description o a generic
reiner0 process. 8a&le +.#!# o t'at c'apter lists a num&er o air&orne emission actors ;kg pollutant
emitted@#$
3
L reiner0 eed: or several pollutants, including particulate matter, *5
-
, C5, '0drocar&ons,
B5,, alde'0des, and ammonia. 8'e total o t'e emission actor values or all process units and or all
pollutants is 66 kg pollutant emitted@#$
3
L reiner0 eed. 8'is data will &e used to estimate t'e cost o
treating t'ese air&orne emissions or t'e reiner0 acilit0.
A t0pical reiner0 mig't &e e,pected to process a&out +$,$$$ &arrels@da0 o crude oil, or in terms o *I
units, ;+$,$$$:;2- gal@&arrel:;3..7+ L@gal: C 7,#$
6
L crude@da0, and to generate #,#$
6
gal wastewater @
.+
da0 ;Amoco@4*E"A "ollution "revention "roPect: *ummar0 o Reiner0 Release Inventor0, 4.*. 1ept. o
commerce, Bational 8ec'nical Inormation *ervice, ")6---7++$, >arc' #66#:.
8a&le #-.. in t'e te,t provides order o magnitude estimates o t'e operating and capital costs per pound
o waste to treat t'e wastewater and air&orne emissions. )ecause t'e emission actors rom A"!2- or
air&orne emissions are or pollutant loading rat'er t'an or t'e total gaseous waste stream, as an
appro,imation we will adopt t'e pollutant loading cost actors listed or wastewater in 8a&le #-.. instead
;capital costs, _$..2@l& pollutantW operating costs, _$.-+@l& pollutant:. In t'e a&sence o more inormation
air&orne cost actors, t'is s'ould provide an order!o!magnitude cost estimate. De can also appl0 t'e
wastewater cost actors assuming total low ;capital costs, _..2,#$
!2
@l& wastewater lowW operating costs,
_..2,#$
!+
@l& wastewater low:.
Air&orne Emissions:
Capital costs C ;_$..2@l& pollutant:;66 kg pollutant@#$
3
L crude oil:;7,#$
6
L crude oil@da0:
C _36$,$$$ ;pro&a&l0 too low:
5perating costs C ;_$.-+@l& pollutant:;66 kg pollutant@#$
3
L crude oil:;7,#$
6
L crude oil@da0:
C _#3-,$$$@da0 ;pro&a&l0 too 'ig':
Dastewater:
Capital costs C ;_..2,#$
!2
@l& wastewater low:;#,#$
6
gal wastewater@da0: C _.2$ ;pro&a&l0 too low:
5perating costs C ;_..2,#$
!+
@l& wastewater low:; #,#$
6
gal wastewater@da0:
C _.2@da0 ;pro&a&l0 too low:.

.. -et revenue change due to (rocess im(rovements
A c'emical manuacturing acilit0 &u0s raw material or _$.6$ per pound and produces 6$ million pounds
per 0ear o product, w'ic' is sold or _$..+ per pound. 8'e process is t0picall0 run at 6$A selectivit0 and
t'e raw material t'at is not converted into product is disposed o at a cost o _$.7$ per pound ;&0
incineration:. A process improvement allows t'e process to &e run at 67A selectivit0, allowing t'e acilit0
to produce 67 million pounds per 0ear o product. D'at is t'e net revenue o t'e acilit0 ;product sales !
raw material costs ! waste disposal costs: &eore and ater t'e c'angeX Kow muc' o t'e increased net
revenue is due to increased sales o product and 'ow muc' is due to decreased waste disposal costsX
5riginal "rocess: 6$A selectivit0.
Bet Revenue ;per l& product: C selling price ! raw matls. cost ! waste treatment costs
C ;_$..+@l& prod.: ! ;#@.6:;_$.6$:@l& prod. ! ;$.##:;_$.6$:@l& prod.
C ;_$..+@l& product ! _$.66.@l& product ! _$.$6.@l& product
C _$.$#.3@l& product
Improved "rocess: 67A *electivit0.
Bet Revenue ;per l& product: C selling price ! raw matls. cost ! waste treatment costs
C ;_$..+@l& prod.: ! ;#@.67:;_$.6$@l& eed: ! ;$.$-:;_$.6$@l& waste:
C ;_$..+@l& product ! _$.6#-@l& product ! _$.$#-@l& product
C _$.#-6@l& product
.6
8'e net c'ange in revenue romto t'is process improvement is due to a reduction in raw materials costs o
_$.$++@l& product and due to a reduction in waste treatment costs o _$.$++@l& product. )ot' actors
contri&ute e9uall0 to t'e en'anced revenue.

0. Estimated #ealth Costs for E1(osure to Elevated 6evels of !ine Particulate Matter
Reduction: 3$$ tons@da0 o ine particulate matter
E,pected )eneits: #. less earl0 deat's@0r, and -2 ewer cases o c'ronic &ronc'itis per 0ear
Costs: _6,$$$,$$$ per earl0 deat' and _3$$,$$$ per case o c'ronic &ronc'itis.
Bet Cost Reduction C ;#. less earl0 deat's@0r:; _6,$$$,$$$ per earl0 deat': G ;-2 c'ronic &ronc'itis cases
per 0ear:;_3$$,$$$ per case o c'ronic &ronc'itis: C _#$6.-,#$
6
@0r.
*ocial Costs "er 8on Emitted: ;_#$6.-,#$
6
@0r:@S;3$$ tons@da0:;36+ da0s@0r:T C F==;.%5?ton.
In 8a&le 3!-. o t'e American Institute o C'emical EngineersF Center or Daste Reduction 8ec'nologies
8otal Cost Assessment >et'odolog0, \ul0 --, #666, a range o 'ealt' costs o cancer was s'own to span
t'e range o _-@ton to tens o millions o dollars@ton o pollutant emitted to t'e air. 8'e value calculated
in t'is pro&lem is wit'in t'at ver0 &road range.

..
Cha(ter '.. 6ife7Cycle Conce(ts$ Product Ste/ardshi($ and Green Engineering

'. 6ife Cycle )nventory for Pa(er versus Plastic Grocery Sac4s
A simpliied diagram o t'e maPor lie c0cle stages or grocer0 sacks is s'own &elow. t'e grocer0 sacks
are rec0cled &ack to t'e use stage o t'e lie c0cle.
8'e inventor0 elements or t'e sack air emissions and energ0 consumption are s'own in t'e ta&le &elow.
a: Eects o rec0cle rate on t'e lie!c0cle air releases and energ0 or plastic and paper sacks.
(unctional 4nit: # paper sack C - plastic sacks
$A Rec0cle Rate:
"aper sack: Air releases C ;$.$+#6 G $.$+#: oJ@sack C $.#$-6 oJ@sack
Energ0 C ;6$+ G .-2: )tu@sack C #,6-6 )tu@sack
"lastic sack: Air releases C -;$.$#26 G $.$$2+: oJ@sack C $.$37- oJ@- sacks
Energ0 C -;262 G #7+: )tu@sack C #,-67 )tu@- sacks
+$A Rec0cle Rate: ;assume no emissions or energ0 or rec0cled sacks:
"aper sack: Air releases C .+;$.$+#6 G $.$+#: oJ@sack C $.$+#3 oJ@sack
Energ0 C .+;6$+ G .-2: )tu@sack C 7#2.+ )tu@sack
"lastic sack: Air releases C ;$.$#26 G $.$$2+: oJ@sack C $.$#6# oJ@- sacks
Energ0 C ;262 G #7+: )tu@sack C 626 )tu@- sacks
#$$A Rec0cle Rate: ;assume no emissions or energ0 or rec0cled sacks:
"aper sack: Air releases C $.$;$.$+#6 G $.$+#: oJ@sack C $.$ oJ@sack
.7
Raw
>aterials
E,traction
>aterials
>anuacture
/rocer0
*ack
>anuacture
/rocer0
*ack 4se
/rocer0
*ack
1isposal
Rec0cle
(ap/r %ac7 (lastic %ac7 (ap/r %ac7 (lastic %ac7
Air 50issions Air 50issions 5n/r6y 5n/r6y
,i./-Cycl/ %ta6/s "o43sac7$ "o43sac7$ "Bt13sac7$ "Bt13sac7$
)at/rials 9 prod1ct )an1.act1r/
9 (rod1ct 1s/ 0.0516 0.0146 905 464
+a; 0at/rials /'traction
9 prod1ct disposal 0.051 0.0045 724 185
Energ0 C $.$;6$+ G .-2: )tu@sack C $.$ )tu@sack
"lastic sack: Air releases C $.$;$.$#26 G $.$$2+: oJ@sack C $.$ oJ@- sacks
Energ0 C $.$;262 G #7+: )tu@sack C $.$ )tu@- sacks
&: "lot air emissions and energ0 as a unction o rec0cle rate
.6
=ir 3missions
0
0.02
0.04
0.06
0.08
0.1
0.12
0 20 40 60 80 100 120
/e,y,le /ate (>)
(ap/r %ac7 (lastic %ac7s "2$
3nergy Consumption
0
400
800
1200
1600
2000
0 20 40 60 80 100 120
/e,y,le /ate (>)
(ap/r sac7 (lastic sac7s "2$
8'e lie!c0cle air emissions and energ0 consumption o plastic sacks are a&out 2$A and 7$A,
respectivel0, o t'ose or paper sacks on an e9ual unctional unit &asis. 5nl0 at #$$A rec0cle are t'e lie!
c0cle inventories e9ual or t'ese c'oices o grocer0 sacks.
c: "aper sacks pro&a&l0 'ave a 'ig'er environmental impact compared to plastic sacks. 8'e air emissions
are signiicantl0 'ig'er and t'e energ0 consumption is slig'tl0 more. Kowever, t'is conclusion is
uncertain &ecause wit' t'e inormation given, it is impossi&le to determine t'e speciic c'emical releases
and t'ereore t'e speciic c'aracteriJation o impacts. *peciic impacts o energ0 consumption will onl0
&e known i t'e uel t0pe is identiied or eac' sack. 8'e composition o t'e air releases or eac' sack is
unknown. 5ne t0pe o sack mig't 'ave signiicant to,ic emissions compared to t'e ot'er sack, w'ic' in
man0 cases would outweig' t'e dierences in mass emission rate.
d: "etroleum consumption comparison: assume $A rec0cle rate
"aper *ack: #$A o energ0 needed to manuacture one paper sack is ossil uel &ased
C ;$.#:;6$+G.-2: )tu@sack C .3.2 )tu
"etroleum re9uired C .3.2 )tu@-$,$$$ )tu@l& petroleum C 3.6.,#$
!3
l& petroleum
- "lastic sacks: $.- l& petroleum needed or energ0 to create # l& pol0et'0lene or sacks
>ass o petroleum e9uivalent or energ0 needs o - sacks C -;262G#7+: )tu@-$,$$$
C 6.+,#$
!-
l& petroleum
8otal mass o petroleum or - sacks
C ;6.+,#$
!-
l& petroleum:;# l& pol0et'0lene@.- l& petroleum: C $.3- l& petroleum
e: Large uncertaint0 in t'e unctional unit e9uivalence will c'ange t'e conclusions o t'is stud0. (or
e,ample, i instead o - plastic sacks &eing e9uivalent to # paper sack, 2 plastic sacks are actuall0 needed,
t'en t'e air emissions and energ0 releases o plastic sacks would &e t'e dominant compared to paper.

%. 6ife7Cycle Assessment of Dia(ering Systems
a: 1iapers per &a&0 per week or disposa&le diapers = E9uivalenc0 o diapers
#+.7 &illion disposa&le diapers are sold annuall0
3,.7.,$$$ &a&ies are &orn eac' 0ear
c'ildren wear diapers or t'e irst 3$ mont's
disposa&le diapers are used on 7+A o c'ildren.
Bum&er o &a&ies in diapers
C ;3,.7.,$$$ &a&ies &orn@0r:;3$ mo. in diapers@#- mo@0r: C 6,26.,+$$
Bum&er o &a&ies in disposa&le diapers
C 6,26.,+$$ &a&ies;$.7+: C 7,$2.,3.+
Bum&er o disposa&le diapers per &a&0 per 0ear
C ;#+.7,#$
6
disposa&le diapers:@;7,$2.,3.+ &a&ies: C #,663.2 disposa&le diapers@&a&0
Bum&er o disposa&le diapers per &a&0 per week
C ;#,663.2 disposa&le diapers@&a&0:@+- weeks C 36.3
E9uivalence C ;36.3 disposa&le diapers@&a&0@wk:@;67 clot' diapers@&a&0@wk: C $.+..
&: Complete t'e 8a&le o Ratio o Impact to Kome Laundered Impact
7$
Impact 1isposa&le
diapers
Commerciall0
laundered clot'
diapers
Kome laundered
Clot' diapers
Energ0 re9uirements ;million )84: $.+- $.++ #.$
*olid waste ;cu&ic eet: 2.-6 #.$ #.$
Atmosp'eric emissions ;l&: $.+$ $.2. #.$
Dater&orne wastes ;l&: $.#2 $.6+ #.$
Dater re9uirements ;gal: $.-7 #.-6 #.$
c: Rec0cle "ercentage or 1isposa&le 1iapers
8'e rec0cle percentage needed or disposa&le diapers to e9ual t'e solid waste re9uirements o laundered
clot' diapers ;-.3 cu&ic eet: can &e o&tained rom t'e &est!it e9uation in t'e igure a&ove. Rearranging
t'e trendline rom a&le and solving or ,, , C ;#..$2!-.3:@$.#63 C 6$.23A.

0. Streamlined !uel 6ife7Cycle Assessment for Conventional Gasoline and Gasohol in *ehicle
Trans(ortation
Conventional gasoline is a &lend o a num&er o crude oil reiner0 products wit' t'e ollowing average
weig't percentages ;aromatics, -7.6AW oleins, #$.7AW &enJene, #.6AW and t'e remainder a mi,ture o
alkanes:. /aso'ol is a &lend o #$A vol. et'anol wit' 6$A vol. conventional gasoline. /aso'ol is used
primaril0 in winter to reduce C5 emissions and smog precursors. 8'e purpose o t'is pro&lem is to
perorm a streamlined lie!c0cle assessment o t'ese two uel t0pes. 8'e scope o t'e assessment will &e
onl0 C5
-
emissions over t'e entire uel c0cle. 5t'er impact categories will &e neglected in t'is anal0sis.
8'e orm o t'e assessment will &e mass o C5
-
per gallon o uel.
7#
0olid ?aste per ' 8iapers
y ! -0.162' 9 17.04
+
2
! 1
0
4
8
12
16
20
0 20 40 60 80 100 120
> /e,y,le
8'e uel c0cle or an0 given transportation uel includes several stages: eedstock production ;i.e. crude
oil production or conventional gasoline or corn production or et'anol:, eedstock transportation and
storage ;8&*:, uel production, uel transportation, distri&ution, and storage ;8*&1:, and uel
com&ustion during ve'icle use. 8'e inventor0 o energ0 utiliJation during t'ese lie!c0cle stages will &e
taken rom t'e document </REE8 #.+ = 8ransportation (uel C0cle >odel: %olume #, >et'odolog0,
1evelopment, 4se, and Results?, Dang, >.Z., 8ransportation 8ec'nolog0 R&1 Center, Argonne
Bational La&orator0 ;www.transportation.anl.gov:.
Conventional Gasoline (CG) Inventory: Basis is 1 gallon
Energ0 eiciencies during various lie!c0cle stages or t'e production o C/ are as ollowsW crude oil
recover0 ;67A:, crude 8&* ;66.+A:, C/ reining ;7+A:, and C/ 81&* ;67.+A:. 8'e overall energ0
eicienc0 is ;.67U.66+U.7+U.67+:;#$$: C 7#.6A rom 8a&le 2.23 o Dang. (or eac' unit o energ0
contained in C/, an additional 9uantit0 o energ0 o magnitude #@$.7#6 = # C $.--+ units is re9uired to
process and transport t'e eed materials. (or eac' gallon o C/, t'e energ0 content is #-$,$$$ )tu@gal
;8a&le 3.3 o Dang:. "er gallon o C/, t'e energ0 needed to process t'is uel is ;$.--+:;#-$,$$$ )tu: C
-.,$$$ )tu. In t'e a&sence o inormation regarding uel t0pe used to satis0 t'is energ0 load, natural gas
will &e assumed since most o t'e energ0 is consumed during reiner0 operations and natural gas is likel0
to &e a maPor component o t'is energ0 consumption. (rom 8a&le 7.3!6 o c'apter 7, t'e emission actor
or C5
-
is $.#- l& C5
-
@ standard t
3
o natural gas and t'e 'eating value o natural gas is #,$$$
)tu@standard t
3
. 8'e total lie!c0cle emissions o C5
-
per gallon o C/ com&usted in ve'icle
transportation is
C ;#-$,$$$G-.,$$$:)tu;# standard t
3
@#,$$$ )tu:; $.#- l& C5
-
@ standard t
3
: C #..6 l& C5
-
.
Gasohol Inventory: Basis is 1 gallon
8a&le 2.-# rom Dang s'ows t'at t'e total corn!to!et'anol energ0 consumption is 2$,$$$ )tu@gallon o
et'anol and t'at 7$A is supplied &0 coal and -$A &0 natural gas. )ecause et'anol is #$A &0 volume
et'anol, 2,$$$ )tu o energ0 per gallon gaso'ol must &e added to t'e contri&ution o C/ to t'e &lend.
8'e contri&ution o C/ can &e calculated rom t'e result a&ove, ;$.6:;#..6 l& C5
-
: C #+.72 l& C5
-
. 8'e
coal contri&ution can &e determined knowing t'e 'eating value o coal ;#-,$$$ )tu@l& coal: and t'e
emission actor or coal ;+,+$$ l& C5
-
@ton coal:. Contri&ution o coal C ;$.7:; 2,$$$ )tu:;# l& coal@#-,$$$
)tu:;# ton@-,$$$ l&:;+,+$$ l& C5
-
@ton coal: C $..3 l& C5
-
. Contri&ution o natural gas C ;$.-:;2,$$$ )tu:
;# standard t
3
@#,$$$ )tu: ;$.#- l& C5
-
@ standard t
3
: C $.#$ l& C5
-
. 8'e total C5
-
inventor0 or gaso'ol
is C #+.7 G $.. G $.# C #6.6 l& C5
-
. 8'is is +..A lower C5
-
emissions over t'e uel lie c0cle compared
to C/.
7-
Cha(ter '0. )ndustrial Ecology

'. 6ist Processes that Produce and Consume These Chemicals
K0drogen: Inormation *ource = Eirk!5t'mer Enc0clopedia o C'emical 8ec'nolog0
.!oce%%e% that on%u(e Hyd!o-en .!oce%%e% that .!oduce 9yp!oduct Hyd!o-en
Keteroatom ;*,B,5: Removal rom (uels Catal0tic Reorming in Reineries
Ammonia s0nt'esis *team "0rol0sis o K0drocar&ons
>et'anol *0nt'esis >et'anol "lant "urge /as
K0drogenations o Edi&le 5ils Et'0lene "lant 8ail /as
(loat glass manuacturing C5 "lant K
-
/as
Electronic industr0 C'loralkali "lant K
-
C'emical *0nt'esis Coke 5ven /as
Bote: Reineries product muc' &0product K
-
, &ut consume a&out t'e same amount o K
-
wit'in t'e
acilit0 in ot'er important reactions. Co!location o ammonia plants wit' met'anol plants is one maPor
application o t'e use o K
-
&0products or industrial s0snt'esis o products.
Ammonia: Inormation *ource = Eirk!5t'mer Enc0clopedia o C'emical 8ec'nolog0
.!oce%%e% that on%u(e A((onia .!oce%%e% that .!oduce 9yp!oduct A((onia
4rea production: C5
-
G-BK
3
BK
-
C5
-
BK
2
Coking o coal: #+!-$A o B in coal BK
3
Bitric Acid production: o,idation o BK
3 8reatment o Reiner0 *our /as: K
-
*GBK
3
Ammonium Bitrate production: KB5
3
GBK
3
Keteroatom ;B: Removal rom (uels
Ammonium *ulate production: K
-
*5
2
G-BK
3
Ammonium "'osp'ate production:
K
3
"5
2
G3BK
3
C'emical E,plosives: -,2!diamino!#,3,+!
trinitrotoluene and ot'ers
(i&ers = "lastics:
Bote: Less t'an #A o ammonia consumption worldwide is satisied using &0product ammonia.
8'ereore, t'ere is little opportunit0 to construct waste to eed stock transormation o industr0 or
ammonia &0products.

%. "alund+org EcoPar4 Analysis
a: Eicienc0 o Energ0 4tiliJation at a "ower "lant
2.+,#$
6
tons coal com&usted@0r
Coal 'eating value C #$,$$$ )tu@l& coal
Energ0 released upon coal com&ustion
C ;2.+,#$
6
tons coal@0r:;-,$$$ l&@ton:;#$,$$$ )tu@l& coal: C 6.$,#$
#3
)tu@0r
73
"ower plant rating C #,+$$ megawatts C +.#-,#$
6
)tu@'r C 2.27,#$
#3
)tu@0r
*tatoil reiner0 steam use
C ;#2$,$$$ tons steam@0ear:;-,$$$ l&@ton:;#,$$$ )tu@l&: C -.7,#$
##
)tu@0r
Bovo Bordisk steam use
C ;-#+,$$$ tons steam@0ear:;-,$$$ l&@ton:;#,$$$ )tu@l&: C 2.3,#$
##
)tu@0r
1istrict 'eating steam use
C ;--+,$$$ tons steam@0ear:;-,$$$ l&@ton:;#,$$$ )tu@l&: C 2.+,#$
##
)tu@0r
(raction o coal energ0:
to power plant ;2.27,#$
#3
)tu@0r:@; 6.$,#$
#3
)tu@0r: C $.267
to *tatoil reiner0 ;-.7,#$
##
)tu@0r:@; 6.$,#$
#3
)tu@0r: C $.$$3#
to Bovo Bordisk ;2.3,#$
##
)tu@0r:@; 6.$,#$
#3
)tu@0r: C $.$$27
to district 'eating ;2.+,#$
##
)tu@0r:@; 6.$,#$
#3
)tu@0r: C $.$$+
8otal rate o energ0 utiliJation ;raction utiliJed:
C $.267 G $.$$3# G $.$$27 G $.$$+ C $.+#$6
&: %aria&ilit0 in Energ0 1emand
1ail0 varia&ilit0:
Electricity demand in largest in the morning, during late afternoon for air conditioning, and in the
evening. Electricity demand will be highest in summer for air conditioning.
Reiner0 demand will &e greatest in t'e summer w'en more automo&ile travel occurs and in
winter mont's w'en residential 'eating needs are greatest.
Bovo Bordisk demand is likel0 'ig'er in t'e winter mont's w'en seasonal illnesses are more
common ;colds:.
1istrict 'eating demand is more in t'e winter mont's.
Response &0 t'e power plant to varia&ilit0 in demand:
8'e varia&ilit0 in demand or electricit0 is t'e most c'allenging pro&lem to deal wit'. /iven t'at
t'e demands or waste 'eat rom t'e power plant is a ver0 small raction o total 'eat availa&le
rom coal com&ustion means t'at meeting t'e c'anging demands o t'ese energ0 sinks will &e
eas0 to ac'ieve.
c: %alue o Residential Keating *ink
1istrict 'eating energ0 demand
C 2.+,#$
##
)tu@0r
%alue o waste steam or district 'eating
C ;2.+,#$
##
)tu@0r:@;#.+,#$
+
)tu@gal 'eating oil:;_-@gal 'eating oil: C _6,#$
6
@0r

.. Co7location ((ortunities for )ndustry from the TR) Data
72
In >ic'igan, t'ere are a num&er o industrial acilities t'at are located in Rouge River. 8'e ollowing list
s'ows several o t'ese acilities t'at could, wit' urt'er consideration, &e connected to s'are materials and
energ0.
#. A>5C5 5IL RI%ER R54/E 8ER>IBAL, -$+ >ARI5B *8., RI%ER R54/E, DA]BE
C54B8], >I, 27-#7
-. 1E8R5I8 E1I*5B ! RI%ER R54/E "5DER "LAB8, # )ELAB/ER "ARE 1R., DA]BE
C54B8], >I, 27-#7
3. EZ4IL5B L4)RICAB8* C5. RI%ER R54/E "LAB8, -2+ >ARI5B A%E., RI%ER R54/E,
DA]BE C54B8], >I, 27-#7
2. (RI8` "R51*., -++ >ARI5B, RI%ER R54/E, DA]BE C54B8], >I, 27-#7
7+

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is t'e mass in is' C ;$.# kg is'@#$

(ma,imum o oral and in'alation weig'ting actor:

. 8'e solution to t'is e9uation su&Pect to t'e initial condition is

can &e solved using t'e result or product concentration a&ove,

3.88(.001) +1(.1 .01)

8'e ma,imum incremental reactivit0 or a c'emical is provide in Appendi, 1, 8a&le 1!2.

8'e ingestion to,icit0 potential is given &0 e9n. ##.3!#2

8'e ingestion to,icit0 potential is given &0 e9n. ##.3!#2

8'e acid rain potentials or a c'emical,

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