Harvard University Science Olympiad
Environmental Chemistry KEY
Team Name: Team Number
Name(s):
Directions:
• Please write all answers clearly; illegible answers will not be scored.
• There is no penalty for wrong answers. Answer every question, even if you aren’t sure if you’re correct.
• Units are required whenever giving a numerical answer. Don’t worry about significant figures.
• Tie breakers are in order: Lab score, FRQ score, MCQ score
• Good luck on the test!
Written by: Phoenix Wu
[email protected] For official use only:
Page: 3 4 5 6 7 8 9 10 12 Total
Points: 16 29 15 17 14 25 25 50 52 243
Score:
ABBREVIATIONS AND SYMBOLS CONSTANTS
amount of substance n Faraday constant F molar mass M
ampere A free energy G mole mol R = 8.314 J mol–1 K–1
atmosphere atm frequency ν Planck’s constant h R = 0.08314 L bar mol–1 K–1
atomic mass unit u gas constant R pressure P
F = 96,500 C mol–1
Avogadro constant NA gram g rate constant k
Celsius temperature °C hour h reaction quotient Q F = 96,500 J V–1 mol–1
centi– prefix c joule J second s NA = 6.022 × 1023 mol–1
coulomb C kelvin K speed of light c
h = 6.626 × 10–34 J s
density d kilo– prefix k temperature, K T
electromotive force E liter L time t c = 2.998 × 108 m s–1
energy of activation Ea measure of pressure mm Hg vapor pressure VP 0 °C = 273.15 K
enthalpy H milli– prefix m volt V 1 atm = 1.013 bar = 760 mm Hg
entropy S molal m volume V
equilibrium constant K molar M year y Specific heat capacity of H2O =
4.184 J g–1 K–1
EQUATIONS
RT −∆H o 1 k2 Ea 1 1
E Eo −
= ln Q =ln K + constant ln=
−
nF R T k1 R T1 T2
1 PERIODIC TABLE OF THE ELEMENTS 18
1A 8A
1 2
H 2 13 14 15 16 17 He
1.008 2A 3A 4A 5A 6A 7A 4.003
3 4 5 6 7 8 9 10
Li Be B C N O F Ne
6.941 9.012 10.81 12.01 14.01 16.00 19.00 20.18
11 12 13 14 15 16 17 18
Na Mg 3 4 5 6 7 8 9 10 11 12 Al Si P S Cl Ar
22.99 24.31 3B 4B 5B 6B 7B 8B 8B 8B 1B 2B 26.98 28.09 30.97 32.07 35.45 39.95
19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36
K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
39.10 40.08 44.96 47.88 50.94 52.00 54.94 55.85 58.93 58.69 63.55 65.39 69.72 72.61 74.92 78.97 79.90 83.80
37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54
Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
85.47 87.62 88.91 91.22 92.91 95.95 (98) 101.1 102.9 106.4 107.9 112.4 114.8 118.7 121.8 127.6 126.9 131.3
55 56 57 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86
Cs Ba La Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
132.9 137.3 138.9 178.5 180.9 183.8 186.2 190.2 192.2 195.1 197.0 200.6 204.4 207.2 209.0 (209) (210) (222)
87 88 89 104 105 106 107 108 109 110 111 112 113 114 115 116 117 118
Fr Ra Ac Rf Db Sg Bh Hs Mt Ds Rg Cn Nh Fl Mc Lv Ts Og
(223) (226) (227) (261) (262) (263) (262) (265) (266) (281) (272) (285) (286) (289) (289) (293) (294) (294)
58 59 60 61 62 63 64 65 66 67 68 69 70 71
Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
140.1 140.9 144.2 (145) 150.4 152.0 157.3 158.9 162.5 164.9 167.3 168.9 173.0 175.0
90 91 92 93 94 95 96 97 98 99 100 101 102 103
Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
232.0 231.0 238.0 (237) (244) (243) (247) (247) (251) (252) (257) (258) (259) (262)
Page 2 Property of ACS USNCO – Not for use as USNCO Local Section
SevenExam after
Lakes March 31, 2021
Invitational 2021
Multiple Choice/Short Answer
1. (3 points) Select all of the following which are a point source of pollution.
A. Agricultural runoff
B. A leaking container
C. snow melt
D. a sunk oil tanker
2. (3 points) Select all of the following which are a nonpoint source of pollution.
A. Agricultural runoff
B. rainfall
C. snow melt
D. a sunk oil tanker
3. (3 points) Select all of the following of these environmental disasters which were responsible for the
founding of Earth Day?
A. Santa Barbara oil spill
B. Cuyahoga River fire
C. BP oil spill
D. Love Canal Disaster
E. Three Mile Island accident
4. (2 points) According to the Operations Manual: Stabilization Ponds, which bacteria are used in the
first and second steps of water stabilization?
A. Cyanobacteria, Methane Bacteria
B. Acid Bacteria, Methane Bacteria
C. Methane Bacteria, Base Bacteria
D. Acid Bacteria, Base Bacteria
E. Cyanobacteria, Acid Bacteria
5. (2 points) According to the Operations Manual: Stabilization Ponds, how often do controlled discharge
ponds generally discharge?
A. once a week
B. once every 6 months
C. once a year
D. once a month
E. every other week
6. (3 points) Who can give NPDES permits?
A. Congress
B. the EPA
C. state governments
D. the President
E. A certified class IV wastewater management operator
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7. (8 points) According to the Operations Manual:Stabilization Ponds, the average domestic sewage with
well-constructed sewers will provide flows of to gallons containing about lbs or
mg/l of BOD per capita per day.
Solution: 2 pts each in order: 75 gal, 100 gal, 0.2 lbs, 240mg/l
8. (2 points) State the name and year the act was passed that the Environmental Protection Agency would
be created.
Solution: 1 pt each 1970, The Reorganization Plan no.3
9. (2 points) According to the Indiana Wastewater Management manual, how many classifications of
wastewater treatment facilities are there?
A. 5
B. 8
C. 10
D. 12
E. 36
10. (5 points) List all the types of classifications, specifying which are for industrial and which are for
municipal facilities.
Solution: All or nothing The municipal classifications are I-SP, I, II, III, and IV. The industrial
classifications are A-SO, A, B, C, and D.
11. (2 points) Select all of the following classifications that a class IV certified operator are certified to
operate.
A. class II
B. class A
C. class A-SO
D. class A-SP
12. (6 points) What do the following acronyms stand for in the CWA? MAHL, NPDES, PSES.
Solution: 2pts each Maximum Allowable Headworks Loading; National Pollutant Discharge Elim-
ination System; Pretreatment Standards for Existing Sources
13. (4 points) According to the Introduction to the National Pretreatment Program, what are priority
pollutants categorized into?
Page 4
Solution: 2pts per category Metals—including lead, mercury, chromium, and cadmium—cannot be
destroyed or broken down through treatment or environmental degradation. Toxic organics—including
solvents, pesticides, dioxins, and polychlorinated biphenyls (PCBs)
14. (2 points) How many priority pollutants does the EPA current
A. 24
B. 56
C. 126
D. 340
E. 229
15. (3 points) Select all of the following ions contribute to water hardness?
A. K+
B. Na+
C. Mg2+
D. Ca2+
E. H+
16. (3 points) Select all of the following which are methods for reducing water hardness
A. boiling the water
B. use a filter
C. add rock salt to the water
D. add activated carbon to the water
17. (4 points) What are some reasons water hardness is undesirable?
Solution: 1 reason for 2 pts, 2 reasons 4 pts, 3 reasons 5 pts; Hard water can interfere with the
action of soaps and detergents and can result in deposits of calcium carbonate, calcium sulphate and
magnesium hydroxide (Mg(OH)2) inside pipes and boilers, causing lower water flows and making
for less efficient heating. The ions in hard water can also corrode metal pipes through galvanic
corrosion. Hard water can appear cloudy if the solubility of mineral salts is exceeded. Furthermore,
if the calcium concentration surpasses 100 ppm, the water will taste “funny.
18. (3 points) What element does the Kjeldahl method test for in water?
A. Oxygen
B. Phosphorus
C. Sulfur
D. Carbon
E. Nitrogen
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19. (3 points) What does an imhoff cone test for?
A. DO
B. BOD
C. settleable solids
D. TDS
E. turbidity
20. (3 points) What is a secchi disk used to test for?
A. turbidity
B. COD
C. TDS
D. Water hardness
E. heavy metals
21. (3 points) What element does the Kjeldahl method test for in water?
A. Oxygen
B. Phosphorus
C. Sulfur
D. Carbon
E. Nitrogen
22. (8 points) The Dumas method tests for the same element as the Kjeldahl method. Briefly explain the
methodology behind the Dumas method.
Solution: Source Wikipedia; The method consists of combusting a sample of known mass to a
temperature between 800 and 900 °C in the presence of oxygen. This leads to the release of carbon
dioxide, water and nitrogen. The gases are then passed over special columns (such as potassium
hydroxide aqueous solution) that absorb the carbon dioxide and water. A column containing a
thermal conductivity detector at the end is then used to separate the nitrogen from any residual
carbon dioxide and water and the remaining nitrogen content is measured.
23. True FALSE A POTW is equipped to handle both domestic and industrial wastes.
24. True FALSE The CWA has been mostly effective in eliminating non-point source pollution
25. True FALSE Class A certified operators are only required to have a highschool diploma or equiv-
alent
26. TRUE False Unlike other environmental programs that rely on federal or state governments to im-
plement and enforce specific requirements, under the National Pretreatment Program
most of the responsibility rests on local municipalities
27. True FALSE Water hardness is considered a potential health risk due to the formation of kidney
stones.
28. TRUE False Septic sewage is generally acidic
Page 6
29. True FALSE Most pollution in the USA is due to point source pollution
30. TRUE False A POTW’s legal authority derives from state law.
31. (14 points) Fill the the following blanks (2pts each)
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FRQs
32. (20 points) Tap water has fluoride added to it to help prevent cavity formation, and the CDC lists water
fluoridation as one of the ten great public health achievements of the 20th century in the U.S. This is
done by maintaining the fluoride levels to 1mg/L. If I have a 100mL sample of tap water and I decide
to slowly add a solution of .1M Mg2+ and .1M Ca2+ , at what volume added solution will there first
be precipitation? What substance will precipitate? MgF2 has a Ksp = 8.0 ∗ 10−8 ; CaF2 has a Ksp =
3.9 ∗ 10–11 . Ignore any acid base properties of F –
Solution: 5pts for species, 15 pts for volume
CaF2 has the lower ksp so it precipitates first. 3.9 ∗ 10–11 = [Ca2+ ][F − ]2
1
1 mg of fluoride per L means 9 ≈ 0.111mM or 0.000111M
If I add x mL of the solution to the tap water, the solution will begin precipitating when 3.9∗10–11 =
0.1x
[ 100+x ][ 0.000111∗100
100+x ]2 ,which when solving for x, gives x = 3.51mL
33. (5 points) How would the results of the previous question change if we did NOT ignore the acid/base
properties of F – ?
Solution: If we do not ignore the acid/base properties, some of the F- will act as a weak base and
abstract hydronium from water to form HF. This means the concentration of F- is actually lower
than the previously calculated amount, so the precipitation happens later.
Page 8
34. (8 points) A natural spring has water which contains a lot of dissolved limestone. As such, it has a lot
of HCO3 – which keeps the pH of the water at certain value. Determine this value. pKa1 = 6.36 and
pKa2 = 10.32 for H2 CO3 .
Solution: pH = pka1 +pka
2
2
= 8.34
For a more detailed explanation, think of the reaction as 2 HCO3 – −−→ H2 CO3 + CO3 2 – . The
Ka2
Keq for this reaction is K a1
. Now, this reaction dominates, meaning that effectively all of the
2–
H2 CO3 and CO3 comes from this dissociation. Therefore, their concentrations are ”equal”. Des-
ignating the original concentration of HCO3 – as x and qthe concentration of H2 CO3 and CO3 2 – as
Ka2 [H2 CO3 ][CO32− ] y2 Ka2 y [CO32− ]
y, we get Ka1 = [HCO3− ]2
= (x−y)2 or equivalently Ka1 = (x−y) = [HCO3− ]
[H + ][CO32− ] √
substituting this back into the Ka2 equation, we get Ka2 = [HCO3− ]
∼ Ka1 Ka2 = [H + ] ∼
pka1 +pka2
pH = 2
35. (17 points) Now if this spring water was used as the tap water in the previous question (not ignoring the
acid/base properties of F – ), how much of the Ca/Mg solution would we need to add before precipitation
occurs? pka HF = 3.8
[H + ][F − ]
Solution: Ka = 10−3.8 = 1.585e − 4 = [HF ]
[F − ] Ka
since pH is buffered at 8.34, [H + ] = 10−8.34 = 4.57e − 9 so that [HF ] = [H + ] = 34673. This means
−
–
that the ratio of F to HF will always stay at this value. To put it another way, FFtotal = 34673+1 34673
=
0.999971. Plugging this back into the formula from the original question ignoring acid/base prop-
0.1x
erties, 3.9 ∗ 10–11 = [ 100+x ][ 0.000111∗100∗0.999971
100+x ]2 gives the answer, which is effectively the same as
the original result of 3.51 mL.
5pts for same volume of solution, 12 pts for reasoning why (8 pts for the correct ratio of F-/F total;
4 pts for substitution back into original equation)
Page 9
Lab Section
Your roommate, a Pre-med student at Harvard is currently struggling in his Organic chemistry class.
He knows that you, who studies environmental chemistry, are quite familiar with titrations, and wants
you to help with his lab report. The assignment is to determine the concentration of a reducing agent,
oxalic acid, by titrating it against KMnO4.
36. (5 points) Balance the reaction between acidified KMnO4 and H2 C2 O4 .
Solution: 2 KMnO4 (aq) + 5 H2 C2 O4 (aq) + 6 H+ (aq) −−→ 10 CO2 (g) + 2 Mn2+ (aq) + 8 H2 O(l) +
2 K+ (aq)
accept without the potassium as well Full points for final reaction + state of matter; half reactions
alone are worth 2 pts; state of matter is worth 1 pt
37. (5 points) You recognize this titration as effectively calculating the COD of a sample of water. Balance
the reaction if we used O2 instead of KMnO4 as the oxidizing agent.
Solution: O2 (g) + 2 H2 C2 O4 (aq) −−→ 4 CO2 (g) + 2 H2 O(l) Full points for final reaction + state of
matter; half reactions alone are worth 2 pts; state of matter is worth 1 pt
38. (40 points) Perform the titration of the oxalic acid solution with KMnO4. Determine the concentration
of oxalic acid and the COD of the solution in mg O2 / L. SHOW ALL EXPERIMENTAL DATA AND
WORK. More space given on the next page. Bonus points + Tie-breaker if you recognize the reference!
Hint, look at the oxalic acid concentration.
Solution: Ideally with 10mL of Oxalic acid you would run 2 trials and average the values. ∼10.24
mL of KMnO4 should be when the endpoint is reached - you are looking for a very light pink color.
10.24mL * 0.1 = 1.024 mmol KMnO4 . KMnO4 reacts with H2 C2 O4 in a 2:5 ratio so there are
1.024 ∗ 25 = 2.56 mmol H2 C2 O4 . 2.56/5 = 0.512 M solution. The reference (+5 pts) is hidden in the
concentration of the H2 C2 O4 ; 5.12 is the course number for Organic Chemistry 1 at MIT!
10.24mL * 0.1 = 1.024 mmol KMnO4 that will react with with 5mL of the oxalic acid solution.
1 mol of KMnO4 has the capability to oxidize 5 mol of electrons, while 1 mol of O2 can oxidize 4
mol of electrons. Therefore, the KMnO4 is equivalent to 1.024∗5
4 = 1.28 mmol of O2.
32g
1.28mmol ∗ mol = 40.96mg O2 per 100mL. Scaling this up by a factor of 200, the COD is 8192
mg/L
Page 10
Solution: more space to solve the question
Page 11
Back in the lab, as part of your homework, you are given a list of field measurements of the transmittances
of a sample of water after it has been diluted multiple times. Use the values to answer the following
questions below. Assume the length of the cuvette is 1cm
Sample % Light Transmitted Absorbance Concentration
A 42.5% 3.1mM
B 21.5% 5.5mM
C 72% 1.2mM
D 0.5mM
39. (5 points) What is the relationship between transmittance and absorbance? Briefly explain and write
the mathematical relation.
Solution: Transmittance is a ratio of the intensity of light before/after traveling through the
medium. Absorbance is a measure of how much light was absorbed by the medium. A = log10 ( T1 )
40. (9 points) Fill in the Absorbance column for samples A-C
41. (15 points) Calculate ϵ for this mystery substance, the equation for the line of best fit, and the r2 value
for this line of best fit.
Solution: KEY FOR Q40 Aa = .372; Ab = 0.668; Ac = .143
L
Using the first value (any value works) A = ϵcd = 0.372 = ϵ ∗ 0.0031 ∗ 1 ∼ ϵ = 120 mol∗cm 4
pt for value (+=5%), 1 pt for unit
Doing statistics gives you y = 122.11x − 0.00483 with a r2 = 0.999968
5pts for equation and r2 all or nothing +=5%
42. (23 points) Using the previously calculated line of best fit, determine the predicted % light transmitted
and absorbance for sample D. Write it in the table. Then graph the standard curve generated with
samples A-C also showing sample D.
Solution: Plugging in .0005M into the previous equation,y = 122.11 ∗ 0.0005 − 0.00483, we get
A = 0.0562 (5pts) Then for the graph, 3 points for each of the following: title, correct axes, correct
units, correct spacing, correct datapoints, correct line of best fit
Page 12
print-graph-paper.com
LAB SETUP INSTRUCTIONS EVENT
SUPERVISOR ONLY
Make stock solutions of KMnO4 and H2 C2 O4 . KMnO4 should be 0.1M and H2 C2 O4 should me 0.512M
(bonus points if you get the reference) Instructions are for 1L of both solutions, scale up/down as needed.
Have plenty of reducing solution on hand (eg Na2 S2 O3 ) as well as NaHCO3 in case any spills happen during
the competition day.
Making Acidified KMnO4
How much KMnO4 depends on how many people are attending. To completely react with the 10mL of oxalic
acid solution that we are giving teams, they will need ∼ 30mL KMnO4 to guarantee that they have enough.
This means 30* # of teams is how much KMnO4 you will need to prepare (in mL).
To make 1 L of the acidified KMnO4 solution, you need 2M H2 SO4 . If you already have 1-2M H2 SO4
solution, use it and skip to the next paragraph; otherwise, this is how you can make 2M solution from stock
96% H2 SO4 .
Making H2SO4 solution
First, MAKE SURE YOU HAVE ACCESS TO PROPER PPE. This means carry out the acid
dilution in a fume hood with goggles, apron, gloves and preferably a faceshield. Make sure you have
NaHCO3 and a sink nearby in case of any accidents. SLOWLY add 100mL of concentrated 96% H2 SO4
to around 800mL of distilled water in a volumetric flask. It is highly recommended to chill the distilled
water or otherwise mix very slowly as the dilution is extremely exothermic.
Adding KMnO4
Once you have your acid solution (around, add 15.8034g KMnO4 (per liter) and mix well. Top off the
volumetric flask to exactly 1 L and your stock solution is done.
Making Oxalic Acid solution
Each team will need 10mL of Oxalic acid solution. Thus 10*# of teams is how much Oxalic acid you will
need to prepare (in mL).
Mixing up Oxalic Acid
To make 1L of 0.512M oxalic acid, you need 46.234g of oxalic acid. Add the oxalic acid to a volumetric flask
and fill up with around 500mLs. Partially filling up the flask will make mixing/dissolving the solution easier
so top it off to 1L once it looks like everything is mostly dissolved.
Setting up burets/glassware
Make sure each team has access to a stand, and clamp the buret onto the it. Make sure the buret tip is
closed and fill up the buret carefully with around 30 mL of the KMnO4 solution using a funnel. As for
glassware, each team should get a small Erlenmeyer flask or small beaker ∼100mL as well as a graduated
cylinder (10-25mL). Inside the graduated cylinder, give each team 10mL of the oxalic acid solution. This
does not have to be super accurate, but keep it within ± .5mL (can use a pipette).
Page 14
Cleanup
KMnO4 is toxic and CAN NOT BE POURED DOWN THE DRAIN . During the event, make sure
you have waste beakers designated and force competitors to dispose of any manganese waste in them includ-
ing waste produced by washing glassware.
KMnO4 can be reduced safely using a number of reducing agents such as H2 O2 or Na2 S2 O3 . Make sure
to not use anything that can react with acid such as NaHSO3 . In fact, you can use any leftover oxalic acid as
a reducing agent as well. Make sure to add any agents that can produce gas slowly, and preferably inside a
fume hood. After all the Mn is in the 2+ state, (the purple color is gone), add NaHCO3 slowly to neutralize
the remaining acid. Properly store the waste in a labeled container and make sure that all chemical species
are listed.
Cleaning the burets and other glassware involves using either a reducing bath or simply washing the
glassware with reducing solution and adding it to the rest of the KMnO4 waste.
Page 15
