13 EnvironmentalChemistry,Ninth Edition,AnswerManual

CHAPTER 3 FUNDAMENTALS OF AQUATIC CHEMISTRY

QUESTIONS AND PROBLEMS
1. Alkalinityis determinedbytitrationwith standardacid. The alkalinity is often expressedas
mg/LofCaC0
3
. If Vp mLofacidofnormalityN arerequiredto titrateVs mLofsampleto
thephenolphthaleinendpoint,whatistheformulaforthephenolphthaleinalkalinityasmg/L
ofCaC0
3
?
Answer: (Vp x N)/Vs
2. Exactly 100 poundsofcane sugar(dextrose), C
12
H
22
0
11
, were accidentally discharged into
a small stream saturated with oxygen from the air at 2Ye. How many liters ofthis water
could be contaminated to thc extent of removing all the dissolved oxygen by
biodegradation?
Answer: Thecalculationis thefollowing, whereDxis dextrose
A
.. <! 4.54xl04 DxxlmolDx x 12mo102x3.20xl04mg02 x lL =6.13xl06L
g 342gDx 1molDx 1mol02 8.32mgO2
--3f-'..-rrf .. Calculatethe ratio [PbT]/[HT2-] for NTA in equilibrium withPbC0
3
in a mediumhaving
[HC0
3
-] = 3.00x 10-
3
M.
Answer: The reaction is PbC0
3
(s) + HT
2
- PbT- + HC0
3
- and, designating the
equilibriumconstantofthisreactionas K, thefollowing applies:
4.06 x 10-
2
= 13.5
3.00 x 10-
3
.......r."If the medium Problem 8 contained excess calcium such that of
o uncomplexedcalcIUm, [Ca
2
+], were5.00 x 10-
3
M, whatwouldbetheratIo [PbT]/[CaT]at
pH7?
Answer: Thereactionis PbC0
3
(s) + Car + H+ Ca
2
+ + HC0
3
- + Pbrforwhich
theequilibriumconstantmaybedesignatedK", whichhas a valueof5.24, and the following
applieswhen[HC0
3
-] = 3.00 x 10-
3
M and[Ca
2
+] = 5.00x 10-
3
M.: Theratiois 0.0349
[PbT] [H+]K" = 0.035
[CaT] [Ca
2
+][HC0
3
-]
wastewaterstream containing 1.00 x 10-
3
M disodium NTA, Na
2
HT, as the only solute
is injected into a limestone (CaC0
3
) formation through a waste disposal well. Aftergoing
through this aquifer for some distance and reaching equilibrium, the water is sampled
through a sampling well. Whatis thereactionbetweenNTA species and CaC0
3
? Whatis
theequilibriumconstantfor thereaction?WhataretheequilibriumconcentrationsofCar,
HC0
3
-,andHT
2
-?(Theappropriateconstantsmaybelookedupinthis chapter.)
Answer: Thereactionis PbC0
3
(s) + HT2- PbT- + HC0
3
- from whichthefollowing
maybecalculated:
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15 EnvironmentalChemistry,NinthEdition,AnswerManual
17. Whatdetrimentaleffectmaydissolvedchelatingagentshaveuponconventionalbiological
wastetreatment?
Answer: The presence ofchelating agents in the sewage mayprevent heavy metals from
beingremovedbythe sewagesludge(biosolids).
18. Whyis chelatingagentusuallyaddedto artificialalgalgrowthmedia?
Answer: Tokeepmicronutrientironinsolution
19. Whatcommoncomplexcompoundofmagnesiumis essentialto certainlifeprocesses?
Answer: Chlorophyll,whichconductsphotosynthesis
20. Whatis alwaystheultimateproductof polyphosphatehydrolysis?
Answer: Orthophosphate,usuallyas H
2
P0
4
- orHPOl-.
21. A solution containing initially 1.00 x 10-
5
M CaT- is brought to equilibrium with solid
PbC0
3
. Atequilibrium,pH= 7.00, [Ca
2
+] = 1.50 x 10-
3
M,and [HC0
3
-] =1.10 x 10-
3
M.
Atequilibrium,whatis thefractionoftotalNTAinsolutionas PbT-?
Answer: The reactionis PbC0
3
(s) + Car + H+ <E--- Ca
2
+ + HC0
3
- + Pbrforwhich
the equilibriumconstantmaybedesignatedK", whichhas avalueof5.24, andthefollowing
applies atpH7.00when[HC0
3
-] = 1.50 x 10-
3
M and [Ca
2
+] = 1.10 x 10-
3
M.:
[Pbr] [Pbr]/[Car]
FractionofNTAas Pbr= =0.318
[Car]+[Pbr] [Car]/[Car]+[Pbr]/[Car]
0.318
----- =0.241
1.000+ 0.318
22. What is the fraction ofNT A present as I-IT
2
- after HT
2
- has been brought to equilibrium
withsolidPbC0
3
atpH7.00 inamediuminwhich[HC0
3
-] = 1.25 x 10-
3
M.
Answer: Thereaction is PbCOls)+HT2- <E--- PbT- +HC0
3
- for whichK = 0.046 and
fromwhichthefollowingmaybecalculated:
4.06x 10-
2
=32.5
1.25 x 10-
3
[HT
2
-]
FractionofNT AasHT
2
- =
[Pbr]+ [HT
2
-]
1.00
----=0.030
32.5 +1.00
23. Describe ways in which measures taken to alleviate water supply and flooding problems
mightactuallyaggravatesuchproblems.
Answer: Diversion ofwater to municipal and irrigation uses has resulted in depletion of
water sourccs and degradationofwaterquality, such as by adding salinity. Constructionof
dikes along rivers to alleviate flooding has resulted in catastrophic flooding when these
structuresfailduringextremeflooding events.
24. The study of water is known as , ,
is the branchofthe science dealing withthe characteristics offresh water, and the science
thatdealswithabout97%ofallEarth'swateris called
Answer: Hydrology, limnology, andoceanography,respectively.
K
16 EnvironmentalChemistry,NinthEdition,AnswerManual
25. Consider the hydrologic cycle in Figure 3.1. List or discuss the kinds or classes of
environmentalchemistrythatmightapplyto eachmajorpartofthis cycle.
Answer: Oceanography applies to water in the ocean, by far the largest amount in the
cycle; atmospheric chemistry interacts with water in the atmosphere, such as in formation
ofcondensationnuclei aroundwhichcloud droplets form; limnology applies to fresh water
in streams and lakes; chemistry of the geosphere interacts with aquatic chemistry in
groundwater; waterinsoilisverymuchinvolvedwithsoilchemistry.
26. Consider the unique and important properties of water. What molecular or bonding
characteristics ofthe water molecules are largely responsible for these properties. List or
describe one ofeach ofthe following unique properties ofwater related to (a) thermal
characteristics,(b)transmissionoflight,(c) surfacetension, (d)solventproperties.
Answer: (a) Thehighheatcapacityand highheats ofvaporizationand fusion ofwater are
due largelyto its hydrogenbondingtendencies; (b) thetransmission oflightis theresultof
the lack ofchromophores that absorb visible light in the water molecule; (c) the high
surfacetensionis largelyduetothestrongbondingofwatermoleculcs witheachother; and
(d) the solventproperties ofwater, such as the high solubility ofionic solutes init, are due
largelyto thepolarnatureofthe watermoleculeanditshydrogen bondingcapability.
27. Discusshowthermal stratificationofabodyofwatermayaffectitschemistry.
Answer: The major effect is the formation ofthe oxygen-deficient hypolimnion bottom
layerinbodiesofwaterinwhichreducedspeciestendto predominate.
28. Relate aquatic life to aquatic chemistry. In so doing, consider the following: autotrophic
organisms, producers, heterotrophic organisms, decomposers, eutrophication, dissolved
oxygen, biochemicaloxygendemand.
Answer: As several examples, photosynthetic autotrophic organisms are producers that
generate biomass that provides the base of the aquatic food web; producers require
adequate nutrients to generate biomass, but ifthe nutrients are excessive, eutrophication
mayrcsult; toomuchbiomass inwatercanresultinexcessivebiochemicaloxygendemand
inwaterwithdepletionofdissolvedoxygen. '
29. Assuminglevels ofatmospheric CO
2
are 390ppmCO
2
, whatis thepHofrainwaterdue to
the presence ofcarbon dioxide? Someestimates are for atmospheric carbon dioxide levels
todoubleinthe future. WhatwouldbethepHofrainwaterifthis happens?
Answer: As noted in Section 3.7, the value of[C0
2
(aq)] inwater at 2YC in equilibrium
with air that is 390 ppm CO
2
is 1.276 X 10-
5
M. In pure rainwater, the carbon dioxide
dissociates partially in water to produce equal concentrations ofHI and HC0
3
- and from
the Ka1 expressionfor CO
2
, [H+] = 2.38 X 10-
6
andpH= 5.62. Doublingatmospheric CO
2
levelswoulddouble the concentrationofCO
2
inrainwaterto 2.552 x 10-
5
M and, as shown
inSection3.7,thisgives [H+] = 3.37 X 10-
6
andpH=5.47.
30. Assume a sewage treatment plant processing 1 million liters of wastewater per day
containing 200 mg/L ofdegradable biomass, {CH
2
0}. Calculate the volume ofdry air at
2YCthat must be pumped into the wastewater per day to provide the oxygenrequired to
degradethebiomass.
Answer: The reaction is {CH
2
0} + 02 --l> CO
2
+ H
2
0.The amount ofbiomasspresent in
the 1 million liters ofeater is 2.00 x 10
8
mg =2.00 x 10
5
g. The moles of02required to
reactwiththisbiomassare
17 EnvironmentalChemistry,NinthEdition,AnswerManual
Since only 20.95% ofdry airis 020 the moles ofairneeded to supply this 02= 3.l8 x 10
4
mole. Thevolumeofthis amountofairat 25C and 1atmpressurecanbe calculatedbythe
ideal gas law, PV = nRT, where R = 0.0821 L atm mor
l
giving 7.78 L ofair. Only a
fraction ofthe oxygen in the air is actually transferred into the sewage, so significantly
moreairwouldneedtobepumpedto supplytheoxygenrequired.
31. Anaerobic bacteria growing in a lake sediment produced equal molar amounts ofcarbon
dioxide and carbon monoxide according to the biochemical reaction 2{CH
2
0} CO
2
+
CH
4
, so thatthewaterinthe lakewas saturatedwithbothCO
2
gas andCH
4
gas. Inunits of
mol x L-1 x atm-
1
the Henry's law constant for CO
2
is 3.38 x 10-
2
and that ofCH
4
has a
value of1.34 x 10-
3
At the depth at which the gas was being evolved, the total pressure
was 1.10 atm and the temperature was 25C, sO the vapor pressure ofwater was 0.0313
atm. CalculatetheconcentrationsofdissolvedCO
2
anddissolvedCH
4
.
Answer: Since equimolar amounts ofCO
2
and CH
4
are evolved, the mole fraction ofeach
gas = 0.500. The partial pressure ofeach gas = 0.500 x 1.10 = 0.550 at111. The corrected
pressure ofeach gas =0.550 - 0.0313 = 0.519. Using Henry's law, [C0
2
] = 0.519 atm x
3.38 x 10-
2
mol xL-1 xatm-
1
=1.75 x 10-
2
Mand[CH
4
] =6.95 x 10-
4
M.