ENGS37 Fall2013

INTRODUCTIONTOENVIRONMENTALENGINEERING

HOMEWORK#2

SOLUTIONS

1.(10points)Abankruptchemicalcompanyhasbeentakenoverbynewmanagement.
On the property they found a 20,000 m
3
brine pond containing 25 g/L of salt and they
propose to flush it through a discharge pipe leading to the Atlantic Ocean, which is
nearby and which has a salinity of 30 g/L. What flow rate of freshwater (in L/s) must
theyusetoreducethesalinityofthepondto500mg/Lwithinoneyear?

DenotethesalinityinthepondbyitstimedependentconcentrationC(t).
Thenmakeamassbudgetwiththecontrolvolumetakenastheentirepond.

Thesaltbudgettakestheform:

KVC S C Q C Q
dt
dC
V
out out in in
+ =
inwhichthesourceS =0becausethereisnochemicalformationofnewsaltinsidethe
pond, and K =0 because there is no reaction that removes salt from inside the pond.
Wealsohave:Q
in
= Q
out
= Q,thevolumetricflowrateoftheflushing,C
in
=0because
the entering water is fresh (no salt content) and C
out
=C(t) since the water being
flushedouthasthesalinityofthewaterinthepond.

Thebudgetthenreducesto:

) (t C Q
dt
dC
V =

Thesolutionofthis1
st
orderdifferentialequationis:

|
.
|

\
|
= = t
V
Q
t C t C exp ) 0 ( ) (

Now,plugthenumbers

|
|
.
|

\
|
= days
m
Q
L mg L mg 365
000 , 20
exp ) / 000 , 25 ( ) / 500 (
3

andsolvefortheflowrateQ.Thesolutionis:

. / 48 . 2
10 4 . 214
4 . 214
3 3
s L
day
L
day
m
Q =

= =

2.(10points)(Mihelcic&Zimmerman,Problem4.5,page154,edited)Inthesimplified
depiction shown below of the Dartmouth ice rink with a Zamboni (iceresurfacing
machine) in operation, points 1 and 2 represent the air intake and exhaust of the
ventilation system, and point 2 the Zambonis tail pipe, which emits carbon monoxide
(CO).GiventhatQ
1
=3.0m
3
/sofairentersatpoint1withaCOconcentrationequalto
10 mg/m
3
, that the Zamboni emits 8 mg/s of CO, and that the volume of the air inside
the ice rink is V = 5.0 x 10
4
m
3
, what is the ultimate CO concentration that can occur
whentheZambonioperatesforaverylongtime?

For this problem, we naturally take the entire volume of air inside the ice rink as the
control volume for the formulation of the budget. The contaminant that we track is
carbonmonoxide,CO.

Thebudgetincludesoneinlet(airintakeatpoint1)withknownflowandconcentration,
one outlet (air exhaust at point 2) with known flow (must be same as intake) and
concentration equal to that found inside the rink, one source (given emission from the
Zamboni)andnodecay.Thus,

S C Q C Q
dt
dC
V + =
3 3 1 1

withV =5.0 x 10
4
m
3
,Q
1
=3.0m
3
/s,C
1
=10mg/m
3
,Q
3
=Q
1
, C
3
=CandS =8mg/s.

Theultimatevalue,thatisreachedafteralongtimeofoperationoftheZamboni,isthat
correspondingtothesteadystate,thatis,whendC/dthasvanished,whichleadstothe
followingreducedbudget:

S C Q C Q + =
1 1 1
0

ofwhichthealgebraicsolutionis:

1
1 1
Q
S C Q
C
+
= .

Pluggingthenumbers,weobtain:

. / 67 . 12
) / 0 . 3 (
) / 8 ( ) / 10 )( / 0 . 3 (
3
3
3 3
m mg
s m
s mg m mg s m
C =
+
=

Note that the volume of air inside the ice rink is irrelevant in steady state. Also note
that the Zamboni only adds a relatively small amount of carbon monoxide to the air
(concentrationrisingfrom10to12.67mg/m
3
).
3.(10points)(modifiedfromNazaroff&AlvarezCohen,Problem3.33,page149)One
ofthemostcommontypesoffertilizersusedbyfarmersisaformofthehighlysoluble
salt ammonium chloride (NH
4
Cl). At a certain farm, water runoff from fields carries
dissolved ammonium chloride to a nearby pond, resulting in a dissolved concentration
ofNH
4
Clinthepondof5mg/L.Atthesametime,ammoniagas(NH
3
)isbeingproduced
by cows that feed around the farmers pond, resulting in an atmospheric level of 500
ppbabovethewatersurface.
Inwater,thefollowingreactionstakeplace

NH
4
ClNH
4
+
+Cl

NH
4
+
NH
3
+H
+

The first equation represents complete dissociation (dissolution of a salt), and the
secondequationisreversiblewithequilibriumconstant[NH
3
][H
+
]/[NH
4
+
]=5.89x10
10

M. Assume that the ambient temperature is 25

o
C and the air pressure is 1 atm.
NeglecttheeffectsofotherimpuritiessuchasCO
2
.

(a)(4points)CalculatethepHofthepondwater.
(b)(4points)Imagineforamomentthatthepondwerecoveredbyalid.Whatwould
thenbetheammoniaconcentration[NH
3
]inthewater?
(c) (2 points) From this thought experiment, what should you conclude, that the pond
exposedtotheairisasourceorasinkofammonia?

(a)pHofthepondwater

Thechemistryofthepondandsurroundingairconsistsofthefollowingelements:

Thefertilizerisasalt,whichdissociatescompletelyinthewater.Thus,

NH4ClNH
4
+
+Cl

While the ammonium ion NH

4
+
undergoes additional chemical changes, the Cl

ion
remainsinactive.ItsconcentrationisthenentirelyduetotheNH
4
Clinput.

Togetthatconcentration,wefirstneedtoconvertthegivenmassamountofNH
4
Clinto
moles.Forthis,webeginwiththemolecularweightofthismolecule:

MWofNH
4
Cl=14+4x1+35.50=53.50g/mol.

ThenumberofmolesofNH
4
Clina5mg/Lsolutionis:

M L mol
mol g
L g
5 5
3
10 35 . 9 / 10 35 . 9
/ 50 . 53
/ 10 5

= =

SinceonemoleculeofNH
4
ClgeneratesoneionofCl

,onemoleofNH
4
Clgeneratesone
moleofCl

,and

[Cl

]=9.35x10
5
M.

AnotherpieceofinformationthatwehaveisthattheNH
3
inthepondisinequilibrium
with an atmospheric concentration of 550 ppb = 550 x 10
9
atm. By virtue of Henrys
Law,withconstantK
H
readfromtableonpage96:

[NH
3
]=K
H
P
NH3
=(62M/atm)(550x10
9
atm)=3.41x10
5
M.

Now,weturntothechemicalreactionsthatoccurinthewater.Therearetwochemical
equilibria

NH
4
+
NH
3
+H
+

H
2
OH
+
+OH

eachwithitsconstantofequilibrium:

2 14
5
5
10
4
10
4
3
10 ] [ ] [
10 73 . 1
10 41 . 3
10 89 . 5
] [
] [
10 89 . 5
] [
] [ ] [
M OH H
NH
H
M
NH
H NH
+

+
+

+
+
=
=

= =

Toclosethesetofequations,weaddtherequirementofelectroneutrality,whichtakes
theform:

[NH
4
+
]+[H
+
]=[Cl

]+[OH

].

Sincewealreadyknow[NH
3
]and[Cl

],wehavethreeequationsforthefollowingthree
unknowns:[NH
4
+
],[H
+
]and[OH

].

WeareafterthepHofthewater,whichdemandsthatweknow[H
+
].Forthis,weneed
toeliminateallotherunknowns.Usingthefirsttwoequationstosolvefor[NH
4
+
]and
[OH

],wesubstituteintotheelectroneutralityequation,toobtain:

] [
10
10 35 . 9 ] [
10 73 . 1
] [
14
5
5 +

+
+ = +
H
H
H
.

ofwhichthesolutionis[H
+
]=1.71x10
9
M.[Theeasiestwaytoobtainthissolutionis
by iterations. Watch out: There is another solution, but it is negative and unphysical.]
ThepHis:

77 . 8 ] [ log
10
= =
+
H pH .

ThispHisabove7(neutralwater),andweconcludethatthepondisalkaline.

(b)Concentrationofammoniaifpondwerecoveredbyalid

If the pond were covered by a lid preventing any exchange with the atmosphere, the
onlynitrogenthatwouldbepresentwouldbethatwhichcamefromthefertilizer.Thus,

NinallitspresentformsisequaltoNinitsinitialform

[NH
4
+
]+[NH
3
]=[NH
4
+
]
initial

=[NH
4
Cl]
=9.35x10
5
M.

To this relation, we add the equilibrium equation for nitrogen (NH

4
+
NH
3
+ H
+
), the
equilibriumequationforwater(H
2
OH
+
+OH

),andelectroneutralityallasbefore
except for Henrys Law because there is no longer any exchange with the atmosphere.
Thisformsasufficientnumberofequationsforthevariousconcentrations.Thesolution
is:

[NH
3
]=2.156x10
7
M,[NH
4
+
]=9.328x10
5
M
[H
+
]=2.548x10
7
M,[OH

]=3.924x10
8
M.

(c)Isthepondexposedtotheairasourceorasinkofammonia?

Becauseoftheexistingexchangewiththeatmosphere,however,theactualamountof
[NH
3
]isthatcorrespondingtoequilibriumwiththeatmosphere:

[NH
3
]=K
H
P
NH3
=(62M/atm)(550x10
9
atm)=3.41x10
5
M

asdoneabove.

Bycomparingthetwoamounts,wefindthatthereismoreNH
3
inthepondwhilebeing
exposed to the air than if it were isolated from the air. In other words, there is more
NH
3
inthepondthanthatprovidedbythefertilizeralone,andthepondhastakenNH
3

fromtheair.Weconcludethatthepondisasinkofammoniadespiteitsowncontent
ofit.

4. (10 points) A 50m thick layer of still air over an industrial area contains a uniform
distributionof2.0mparticlesataconcentrationof90g/m
3
.Thisisinexcessofthe
24hour PM
2.5
threshold of 65 g/m
3
. (PM stands for Particle Matter, and the 2.5
subscript refers to particles 2.5 m in diameter or smaller.) The air inside this layer is
constantlywellmixedbywinds,whiletheairabove50misperfectlycleanandstill.
Because particles are heavier than air (particle density = 800 kg/m
3
whereas air
density = 1.20 kg/m
3
), particles fall and settle on the ground, where they stick and are
notresuspended.Thereisthusanetfluxofparticlesoutoftheairshed.

(a) (2points)DoessettlingfollowStokesorNewtonsLaw?
(b) (4 points) How long does it take for the atmospheric PM concentration at ground
leveltodropbelowthecompliancethreshold?
(c) (4points)Howlongwouldittakefortheairtobecleanifitwerecalmandwehad
towaitfora50mhighparticletofalltotheground?

The control volume for the airshed is of an arbitrary area, A, and a height of 50 m as
depictedbelow.

(a)DoessettlingfollowStokesorNewtonsLaw?

With a diameter of d
p
= 2.0 m, the particles are rather small, and we guess that they
aresmallenoughtofollowtheStokesregime.Inthiscase,theirsettlingspeedisgiven
by:

|
|
.
|

\
|
=
f
f p p c
p
gd C
V

18
2
.

The particle diameter is larger than 1 micron, and we can ignore the Cunningham slip
(thustakingC
c
=1).Pluggingvaluesintheformula,weobtain:

. / 10 67 . 9
) /( 10 8 . 1
/ 20 . 1 800
18
) 10 0 . 2 )( / 81 . 9 )( 1 (
5
5
3 2 6 2
s m
s m kg
m kg m s m
V
p

=
|
|
.
|

\
|


=

Now that we have the settling speed, we ought to check on the Reynolds number to
ensurethatweareindeedintheStokesregime:

. 10 29 . 1
)) /( 10 8 . 1 (
) / 10 67 . 9 )( 10 0 . 2 )( / 20 . 1 (
Re
5
5
5 6 3

=


= =
s m kg
s m m m kg
V d
f
p p f
p

This value fall below 0.3, and we are indeed in the Stokes regime. Thus, the particles
settleataspeedV
p
=9.67x10
5
m/s.

Note:HadweinsteadassumedNewtonsLaw,wewouldhaveobtained:

, / 198 . 0
20 . 1
20 . 1 800
) 10 0 . 2 )( / 81 . 9 )( 0 . 3 (
0 . 3
6 2
s m
m s m
gd V
f
f p
p p
=
|
.
|

\
|
=

withcorrespondingReynoldsnumber

026 . 0
)) /( 10 8 . 1 (
) / 198 . 0 )( 10 0 . 2 )( / 20 . 1 (
Re
5
6 3
=


= =

s m kg
s m m m kg
V d
f
p p f
p

which is not higher than 1000, thus violating the requirement for being in the Newton
regime.

(b) Time it takes for the atmospheric PM concentration at ground level to drop below
thecompliancethreshold

Theairisinastateofturbulence,andthismeansthattheairshedawellmixedvolume.
Weestablishthemassbudgetforthecontrolvolumeoftheairshed:

Sink Source C Q C Q
dt
dC
V
out out in in
+ E E = .
Here V is the volume of the airshed,
dt
dC
0 since the concentration decreases with
time, the term
in in
C Q E = 0 since there is no inflow to the system, C Q C Q
settling out out
= E ,
andboththesourceandsinktermsarezero.So,themassbudgetreducesto

C Q
dt
dC
V
settling
= .

Now,wecansubstituteknownvaluesforunknownvariablebysubstitutingV =A Hand
Q
settling
= A V
p

C AV
dt
dC
AH
p
= .

Manipulatingthisequation,wefind
C
H
V
dt
dC
p
= .

Thesolutiontothisdifferentialequationis

|
|
.
|

\
|
= = t
H
V
t C t C
p
exp ) 0 ( ) ( .

At the starting time (t =0), the concentration in the airshed is C(t =0) =90 g/m
3
as
givenintheproblem.

Theconcentrationattimet isC(t) =thresholdvalue=65g/m

3
,sincewearetryingto
findhowlongittakesfortheconcentrationtodropbelowthisvalue.

Now,plugintheknownvaluesandsolvefort
|
|
.
|

\
|
=

) 50 (
) / 10 67 . 9 (
exp ) / 90 ( ) / 65 (
5
3 3
m
t s m
m g m g

|
.
|

\
|
=

90
65
ln
) 50 (
) / 10 67 . 9 (
5
t
m
s m

t=168,188s=46.7hoursalmost2days.

(c)Timeittakesfortheairtobecleanifitwerecalm

Iftheairwerenotturbulent,thenparticleswouldgentlysettle.Thismeansthatthelast
particlestoreachthegroundwouldbetheonesstartingthehighest,thatis,from50m
high.

The time it takes for these particles to fall depends on the vertical falling speed of
s m
5
10 67 . 9

ascalculatedpreviously.Wecansolvethiswithsimplephysics

days days hours s

V
H
t
p
calm
6 98 . 5 6 . 143 830 , 516 ~ = = = = .

Theextrathinkingquestion
(10points)

Find in a newspaper or other news outlet, on the web or elsewhere, a recent article
dealingwithanenvironmentalissueinwhichacertainphysicaldomainisinvolved,such
astheinteriorofabuilding,anestuaryorotherbodyofwater,andtaketheperspective
ofanenvironmentalengineerwhoiscalledtostudytheproblem.
What control volume will you choose for the study? And, for this control
volume, will you assume that it behaves as a continuously mixed flow reactor or as a
plugflow?Why?

Answerwillvarywiththestudent.Gradingfollowsthefollowingattributes:

2pointsforchoiceofarticlefromtheperspectiveofsuitabilityforthequestionsasked;
2pointsformeaningfulchoiceofcontrolvolume;
3pointsforcorrectnessofwhetherthesystembehavesasaCMFRorPFR;
3pointsforjustificationofbehavior.

2pointssubtractedifeventreportedismorethan35yearsold.