2017 U.S.

NATIONAL
CHEMISTRY OLYMPIAD
NATIONAL EXAM - PART II
Prepared by the American Chemical Society Olympiad Examinations Task Force

OLYMPIAD EXAMINATIONS TASK FORCE

Seth N. Brown, Chair, University of Notre Dame, Notre Dame, IN
James Ayers, Colorado Mesa University, Grand Junction, CO
Mark DeCamp, University of Michigan, Dearborn, MI (retired)
Marian DeWane, Centennial High School, Boise, ID
Xu Duan, Holton-Arms School, Bethesda, MD
Valerie Ferguson, Moore HS, Moore, OK
Julie Furstenau, Thomas B. Doherty HS, Colorado Springs, CO
Kimberly Gardner, United States Air Force Academy, CO
Paul Groves, South Pasadena HS, South Pasadena, CA
David W. Hostage, Taft School, Watertown, CT
Dennis Kliza, Kinkaid School, Houston, TX
John Kotz, State University of New York, Oneonta, NY (retired)
Jane Nagurney, Scranton Preparatory School, Scranton, PA
Sheila Nguyen, Cypress College, Cypress, CA
Ronald Ragsdale, University of Utah, Salt Lake City, UT (retired)

DIRECTIONS TO THE EXAMINER – PART II

Part II of this test requires that student answers be written in a response booklet with blank pages. Only this "Blue Book" is graded for
a score on Part II. Testing materials, scratch paper, and the "Blue Book" should be made available to the student only during the
examination period. All testing materials including scratch paper should be turned in and kept secure until April 24, 2017, after which
tests can be returned to students and their teachers for further study.
Allow time for the student to read the directions, ask questions, and fill in the required information on the "Blue Book". When the
student has completed Part II, or after one hour and forty-five minutes have elapsed, the student must turn in the "Blue Book", Part II
of the testing materials, and all scratch paper. Be sure that the student has supplied all of the information requested on the front of the
"Blue Book," and that the same identification number used for Part I has been used again for Part II.
There are three parts to the National Olympiad Examination. You have the option of administering the three parts in any order, and you
are free to schedule rest breaks between parts.
Part I 60 questions single-answer multiple-choice 1 hour, 30 minutes
Part II 8 questions problem-solving, explanations 1 hour, 45 minutes
Part III 2 lab questions laboratory practical 1 hour, 30 minutes

A periodic table and other useful information are provided on page two for student reference.

Students should be permitted to use non-programmable calculators. The use of a programmable calculator, cell phone, or any
other device that can access the internet or make copies or photographs during the exam is grounds for disqualification.

DIRECTIONS TO THE EXAMINEE

DO NOT TURN THE PAGE UNTIL DIRECTED TO DO SO. Part II requires complete responses to questions involving problem-
solving and explanations. One hour and forty-five minutes are allowed to complete this part. Be sure to print your name, the name of
your school, and your identification number in the spaces provided on the "Blue Book" cover. (Be sure to use the same identification
number that was coded onto your Scantron sheet for Part I.) Answer all of the questions in order, and use both sides of the paper. Use
separate sheets for scratch paper and do not attach your scratch paper to this examination. When you complete Part II (or at the end of
one hour and forty-five minutes) you must turn in all testing materials, scratch paper, and your "Blue Book". Do not forget to turn in
your U.S. citizenship/Green Card Holder statement before leaving the testing site today.
Property of ACS USNCO – Not for use as USNCO National Exam after April 24, 2017
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 ABBREVIATIONS AND SYMBOLS CONSTANTS
amount of substance n Faraday constant F molar mass M
R = 8.314 J mol– K–
1 1
ampere A free energy G mole mol
atmosphere atm frequency  Planck’s constant h R = 0.08314 L bar mol– K–
1 1

atomic mass unit u gas constant R pressure P

F = 96,500 C mol–
1
Avogadro constant NA gram g rate constant k
F = 96,500 J V–1 mol–
1
Celsius temperature °C hour h reaction quotient Q
NA = 6.022  1023 mol–
1
centi– prefix c joule J second s
coulomb C kelvin K speed of light c
h = 6.626  10–34 J s
density d kilo– prefix k temperature, K T
c = 2.998  108 m s–
1
electromotive force E liter L time t
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 Specific heat capacity of H2O =
4.184 J g– K–
1 1

EQUATIONS

RT  H o   1  k  E  1 1 
E  Eo  ln Q ln K       constant ln  2   a   
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)

Property of ACS USNCO – Not for use as USNCO National Exam after April 24, 2017 Page 2
1. [12%] A compound used as a fertilizer contains only the elements C, H, N, and O.
a. Combustion of 1.000 g of the fertilizer in an oxygen atmosphere produces 0.5637 g CO2, 0.6924 g H2O, and 0.3589 g N2.
What are the mass percentages of C, H, and N in the fertilizer?
b. Give the empirical formula of the fertilizer.
c. A solution of 1.000 g of the fertilizer dissolved in 20.00 g water has a freezing point of –2.38 ºC. What is the apparent molar
mass of the fertilizer? Combined with the result in (b), what is the implication of this molar mass? (For water, the freezing
point depression constant Kf = 1.86 ºC/m.)
d. Propose a structure for the fertilizer compound.

2. [12%] Consider these reactions among copper and iodine compounds (all reactions at 298 K):
CuI(s) Cu+(aq) + I –(aq) Ksp = 1.2  10–12
–
+
Cu (aq) + 2 I (aq) CuI2–(aq) Kf = 7.1  108
–
Cu (aq) + 2 e  Cu(s)
2+
Eº = +0.337 V
Cu2+(aq) + e–  Cu+(aq) Eº = +0.159 V
I2(s) + 2 e–  2 I –(aq) Eº = +0.540 V
a. Calculate the number of moles of copper that dissolve if 1.00  10–3 mol CuI(s) is suspended in 1.00 L of solution.
b. Calculate the minimum number of moles of NaI that would need to be added to the mixture in (a) to fully dissolve the CuI.
You may assume that the volume remains 1.00 L.
c. Calculate Keq for the (favorable) disproportionation of aqueous Cu + ion in neutral solution:
2 Cu+(aq) Cu2+(aq) + Cu(s)
d. Copper(II) iodide, CuI2, is not stable. Write a reasonable chemical reaction that describes the decomposition of CuI 2 in
aqueous solution, and show that this is a spontaneous reaction under standard conditions.

3. [13%] The initial rate of decomposition of ozone to molecular oxygen has been examined under a variety of conditions by
measuring the change in pressure as the reaction takes place.
2 O3(g)  3 O2(g)
At 90 ºC, in the presence of relatively small amounts of O3 compared to O2 (present in constant amount), the following data were
obtained:
p(O3), mm Hg ∆P/∆t, (mm Hg) s–1
7.9 1.21  10–3
17.7 5.8  10–3

a. If the pressure changes at a rate of 1.21  10–3 (mm Hg) s–1 at 90 ºC, what is the rate of disappearance of O3 in mol L–1 s–1?
b. What is the order in O3 under these conditions?
Under slightly different conditions, with the initial pressures of O3 held constant, the initial rates were measured as a function
of O2 pressure at 90 ºC and at 100 ºC:

p(O2), mm Hg ∆P/∆t, (mm Hg) s–1, at 90 °C ∆P/∆t, (mm Hg) s–1, at 100 °C
200 3.30  10–3 7.4  10–3
400 1.45  10–3 3.64  10–3

c. What is the order in O2?

d. What is the activation energy for the reaction?
e. The following mechanism has been proposed for the reaction:
k1
O3(g) O2(g) + O(g)
k–1
k2
O(g) + O3(g) 2 O2(g)
Using the steady-state approximation, derive the rate law predicted by this mechanism. Under what circumstances, if any, is
this consistent with the experimental data?
Page 3 Property of ACS USNCO – Not for use as USNCO National Exam after April 24, 2017
4. [13%] Consider the dimerization of nitrogen dioxide:
2 NO2(g) N2O4(g)
Thermodynamic data are given below for the gaseous species at 298 K, except for the heats of vaporization, which are for the
liquids:
NO2 N2O4
∆Hºf, kJ mol–1 33.2 11.1
–1 –1
Sº, J mol K 240.1 304.4
Cp, J mol–1 K–1 37.2 79.2
–1
∆Hºvap, kJ mol 27.7 38.1

a. Calculate ∆Hºrxn, ∆Sºrxn, and ∆Gºrxn for the dimerization of NO2(g) at 298 K.
b. Calculate Keq for the dimerization of NO2(g) at 298 K.
c. Would Keq for the dimerization at 308 K be greater than, less than, or equal to Keq at 298 K? Justify your answer based on the
above data.
d. Would ∆Hºrxn at 308 K be greater than, less than, or equal to ∆Hºrxn at 298 K? Justify your answer based on the above data.
e. Would ∆Hºrxn in the liquid phase be greater than, less than, or equal to ∆Hºrxn in the gas phase? Justify your answer based on
the above data.

5. [12%] Write net equations for each of the reactions below. Use appropriate ionic and molecular formulas but omit formulas for
all ions or molecules that do not take part in a reaction. Write structural formulas for all organic substances. You need not balance
the equations.
a. Solutions of sodium sulfate and lead(II) nitrate are mixed.
b. Aluminum foil is added to concentrated sodium hydroxide solution.
c. Mercury(II) oxide is heated.
d. Sodium is added to 2-butanol.
e. Nitrosyl fluoride and boron trifluoride vapors are co-condensed.
f. Fluorine-18 emits a positron.

6. [12%] Silicon is an industrially important semiconductor with the cubic unit cell shown below (Si atoms represented as black
spheres):

a. How many Si atoms are contained in this unit cell?

b. The length of the edge of the unit cell is 0.543 nm. Calculate the density of silicon in g cm –3.
Semiconductors like Si have an electronic structure characterized by a band of nominally filled orbitals (the “valence band”)
separated from a band of nominally empty orbitals (the “conduction band”) by an energy gap called the “band gap” of the
semiconductor. Conduction arises in a pure semiconductor when there is thermal promotion of an electron from the valence to the
conduction band; both the electron in the conduction band and the vacancy (“hole”) in the valence band are efficient carriers for
electrical conduction.
c. Diamond, silicon, and germanium all have the same structure, but the band gap decreases in the order C (diamond) >> Si >
Ge. Explain the trend in the size of the band gap.
d. Substituting just a few parts per million of B into Si results in a dramatic increase of electrical conductivity compared to
ultrapure Si. Explain why.

Property of ACS USNCO – Not for use as USNCO National Exam after April 24, 2017 Page 4
7. [14%] Oxygen and sulfur form a number of binary fluorides.
a. Draw the Lewis structure of dioxygen difluoride, O 2F2, and sketch or describe the three-dimensional shape of this polar
molecule.
b. Explain why the O–F bonds in dioxygen difluoride, O2F2 (157.5 pm) are much longer than those in oxygen difluoride, OF2
(140.5 pm).
c. Disulfur difluoride, S2F2, exists as two structural isomers. One isomer is analogous in structure to dioxygen difluoride, O2F2,
but the second, more thermodynamically stable isomer, has a structure in which the two sulfur atoms are in different chemical
environments. Draw a Lewis structure of the more stable isomer of disulfur difluoride, S2F2, and sketch or describe its three-
dimensional shape.
d. Sulfur difluoride, SF2, is very unstable, converting to disulfur tetrafluoride, S2F4, in which all four fluorines are in different
environments. Clearly show a chemically reasonable three-dimensional structure of disulfur tetrafluoride, S2F4, and explain
how the structure accounts for the inequivalence of all four fluorine atoms.
e. Sulfur tetrafluoride, SF4 (bp –38 ºC), has a higher boiling point than sulfur hexafluoride, SF 6 (bp –64 ºC). Explain why sulfur
tetrafluoride, SF4, is less volatile than sulfur hexafluoride, SF6.

8. [12%] tert-Butylbenzene is nitrated to give predominantly para-tert-butylnitrobenzene (A), with only small amounts of the meta
(A') and ortho (A'') isomers.

a. Explain why the meta isomer (A') is a minor product in this reaction.
b. Explain why the ortho isomer (A'') is a minor product in this reaction.
c. Give a structure for synthetic intermediate B and propose a reagent or set of reagents X for the transformation of B to para-
tert-butylacetanilide (C).

d. Propose a synthesis of tert-butylbenzene from benzene and any other necessary reagents.

Page 5 Property of ACS USNCO – Not for use as USNCO National Exam after April 24, 2017
 2017 USNCO Part II Exam Answers

1. a. 0.5637 g CO2  (12.01 g C/44.01 g CO2) = 0.1538 g C, 15.38% C

0.6924 g H2O  (2.016 g H/18.016 g H2O) = 0.07748 g H, 7.75% H
0.3589 g N2 = 35.89% N

b. %O = 100% – (15.38% + 7.75% + 35.89%) = 40.98% O

So in 100 g fertilizer there would be:
15.38 g C/(12.01 g mol-1) = 1.28 mol C
7.748 g H/(1.008 g mol-1) = 7.69 mol H
35.89 g N/(14.01 g mol-1) = 2.56 mol N
40.98 g O/(16.00 g mol-1) = 2.56 mol O
Dividing by 1.28 mol gives an empirical formula CH6N2O2.

c. 2.38 ºC/(1.86 ºC/m) = 1.28 m solution

(1.28 mol/1000g H2O)•(20 g H2O) = 0.0256 mol solute
1.000 g solute/0.0256 mol solute = 39.1 g mol-1.
From the empirical formula, the formula mass is 78.1 g mol-1! This says that the
molar mass appears to be half the formula mass; the only way this is possible is if each
mol of fertilizer gives rise to two moles of particles. Thus, the fertilizer is likely an ionic
compound.

d. The most likely cation given the formula is ammonium ion, which leaves an ion with the
formula CH2NO2. Several chemically plausible structures can be written, but the only
one where the anion is not so basic that it would deprotonate the ammonium ion is
carbamate, NH2CO2–. (The only other chemically reasonable alternative is hydrazinium
formate, (NH2NH3+)(HCOO–).) Ammonium carbamate is a common fertilizer.

Fertilizer =

2. a. [Cu+] = [I–] in this solution, and [Cu+][I–] = Ksp = 1.2  10-12

[Cu+] = 1.1  10-6 M, so 1.1  10-6 mol Cu dissolve in 1.00 L.
(Because the [I–] is so low, there is a negligible amount of CuI2– present:
[CuI –2 ]
+ – 2
= 7.1´108 , so [CuI2–]/[Cu+] = 8.6  10-4 if [I–] = 1.1  10-6 M)
[Cu ][I ]
b. The major reaction that takes place is
CuI(s) + I–(aq) CuI2–(aq) Keq = Ksp•Kf = 8.5  10-4
Since almost all the Cu in solution is complexed, [CuI2–] = 1.00  10-3 M.
[CuI –2 ] [1.00 ´10-3 ]
–
= –
= 8.5´10-4
[I ] [I ]
[I–] = 1.18 M
Only 1.00  10-3 mol iodide has bonded to the copper, which is negligible compared to
the amount found free in solution. So 1.18 mol NaI needs to be added to dissolve the
CuI.
c. 2 Cu+(aq)  2 Cu2+(aq) + 2 e– Eº = –0.159 V
Cu2+(aq) + 2 e–  Cu(s) Eº = +0.337 V
2 Cu+(aq)  Cu(s) + Cu2+(aq) Eº = 0.178 V
-1 -1 -1
∆Gº = –nFEº = –(2)(96.485 kJ V mol )(0.178 V) = –34.3 kJ mol
Keq = e–∆Gº/RT = e(34300 J mol-1)/(8.314 J mol-1 K-1)(298 K) = 1.05  106

d. Net reaction: Cu2+(aq) + 2 I–(aq)  CuI(s) + 0.5 I2(s)

This can be written as a sum of two reactions:
(I) A redox reaction:
Cu2+(aq) + I–(aq)  Cu+(aq) + 0.5 I2
∆Gº = –(1)(96.485 kJ V-1 mol-1)(0.159 V – 0.540 V) = +36.8 kJ mol-1
(II) A precipitation reaction:
Cu+(aq) + I–(aq)  CuI(s)
∆Gº = –RTln(Keq) = –(0.008314 kJ mol-1 K-1)(298 K)ln(1/Ksp) = –68.0 kJ mol-1

Thus the net reaction has ∆Gº = +36.8 kJ mol-1 + (–68.0 kJ mol-1) = –31.2 kJ mol-1, and is
spontaneous (under standard conditions).

3. a. With each mol of O3 that reacts of the reaction, 0.5 mol of additional total gas is
produced. So if the total pressure is increasing by 1.21  10-3 (mm Hg) s-1, then the
pressure of O3 is decreasing by twice this, or 2.42  10-3 (mm Hg) s-1. To convert to mol
L-1 s-1, one needs to convert mm Hg to mol L-1 at 90 ºC:
PV = nRT
n/V = P/RT
n/V = (2.42  10-3 mm Hg)/(62.4 [mm Hg] L mol-1 K-1)(363 K)
n/V = 1.07  10-7 mol L-1
So the rate of disappearance of O3 is 1.07  10-7 mol L-1 s-1.

b. When O3 pressure increases by a factor of 2.24, the rate increases by a factor of 4.79,
close to (2.24)2 = 5.01. So the reaction is second order in O3 under these conditions.

c. Doubling the O2 pressure results in roughly a factor of two decrease in the rate. Thus the
order in O2 is –1.

d. ln(k2/k1) = (Ea/R)(1/T1 – 1/T2)

ln(3.64  10-3/1.45  10-3) = (Ea/8.314 J mol-1 K-1)(1/363 K – 1/373 K)
Ea = 104 kJ mol-1 (using the data from 200 mm Hg O2 gives 90.9 kJ mol-1)

e. Applying the steady-state approximation to [O] gives:

k1[O3] = k–1[O][O2] + k2[O][O3]
k1[O3 ]
[O] =
k-1[O2 ]+ k2 [O3 ]
k1k2 [O3 ]2
Rate = k2[O3][O] =
k-1[O2 ]+ k2 [O3 ]
 This is consistent with the experimental data if k–1[O2] >> k2[O3]. This is likely to be
fulfilled under these conditions of relatively high O2 pressure and low O3 pressure.

4. a. ∆Hº = 11.1 kJ mol-1 – 2(33.2 kJ mol-1) = –55.3 kJ mol-1

∆Sº = 304.4 J mol-1 K-1 – 2(240.1 J mol-1 K-1) = –175.8 J mol-1 K-1
∆Gº = ∆Hº – T∆Sº = –55.3 kJ mol-1 –(298 K)(–0.1758 kJ mol-1 K-1) = –2.9 kJ mol-1

b. ∆Gº = –RTln(Keq)
ln(Keq) = –(–2900 J mol-1)/(8.314 J mol-1 K-1)(298 K) = 1.17
Keq = 3.2

c. The reaction is exothermic, so Keq will decrease as the temperature is increased.

d. From the thermochemical cycle:

∆Hºrxn (298 K)
298 K 2 NO2(g) N2O4(g)

∆H = –2C p(NO2)•(10 K) ∆H = C p(N2O4)•(10 K)

∆Hºrxn (308 K)
308 K 2 NO2(g) N2O4(g)
∆Hºrxn (308 K) = ∆Hºrxn (298 K) + 10 K(Cp[N2O4] – 2Cp[NO2])
Since Cp[N2O4] – 2Cp[NO2] = 4.8 J mol-1 K-1 is positive, then ∆Hºrxn (308 K) will be
greater (more positive) than ∆Hºrxn (298 K), although the difference is rather small.

e. An analogous thermochemical cycle . . .

∆Hºrxn (g)
gas 2 NO2(g) N2O4(g)

∆H = 2∆Hvap(NO2) ∆H = –∆Hvap(N2O4)

∆Hºrxn (l)
liquid 2 NO2(l) N2O4(l)
. . . establishes that ∆Hºrxn (l) = ∆Hºrxn (g) + 2∆Hvap(NO2) – ∆Hvap(N2O4).
Since 2∆Hvap(NO2) – ∆Hvap(N2O4) = 17.3 kJ mol-1 is positive, then ∆Hºrxn (l) will be
greater (more positive) than ∆Hºrxn (g).

5. a. Pb2+(aq) + SO42-(aq)  PbSO4(s)

b. Al(s) + 3 H2O(l) + OH–(aq)  Al(OH)4–(aq) + 3/2 H2(g)

c. HgO(s)  Hg(l) + 1/2 O2(g)

Na(s) +
d.

e. NOF(g) + BF3(g)  [NO][BF4](s)

f. 18
F  18O + +

6. a. There are 8 Si atoms in the unit cell.

b. V = (0.543  10-7 cm)3 = 1.60  10-22 cm3

mass = 8  (28.09 g mol-1)/(6.022  1023 mol-1) = 3.73  10-22 g
density = 3.73  10-22 g/1.60  10-22 cm3 = 2.33 g cm-3

c. The filled valence band consists of -bonding orbitals, while the empty conduction band
consists of -antibonding orbitals. Thus, the stronger the bonding, the larger the band
gap. The smaller elements form shorter, stronger bonds (C–C >> Si–Si > Ge–Ge), so the
band gaps also decrease in this order.

d. Replacing a Si atom (with 4 valence electrons) with a B atom (3 valence electrons)

decreases the electron count by one without changing the number or type of orbitals.
Thus each B atom leads to a vacancy in the valence band. These "holes" are good charge
carriers, and so even a small number of boron atoms lead to a relatively large number of
charge carriers (and hence high conductivity) compared to pure Si, where the only charge
carriers arise from thermal excitation.

7. a. In FOOF, each oxygen is bent, and the two FOO planes are roughly perpendicular to one
another:


b. Electron donation from the oxygen lone pairs in FOOF into the O–F * orbitals
("negative hyperconjugation") lengthens the O–F bond (and shortens the O–O bond,
which at 121.7 pm is much shorter than the O–O single bond in H2O2, 147.4 pm, and is
almost the same length as the double bond in O2, 121 pm!):

c. The stable isomer of S2F2 is pyramidal:

d. The four-coordinated sulfur has a "see-saw" geometry, with the equatorial fluorine
distinct from the two axial fluorines. (Obviously the fluorine on the divalent sulfur is
distinct from the other three as well!) The two axial fluorines are not equivalent because
the S–F bond on the divalent sulfur is pointed toward one of them and away from the
other one:
e. SF4, because of its see-saw geometry, has a dipole moment, while SF6, which is
octahedral, does not. The favorable dipole-dipole interactions increase the boiling point
of SF4 compared to SF6. (The greater number of electrons in SF6 would be expected to
give it greater London dispersion forces compared to SF4, but the lower polarizability due
to the higher oxidation state in SF6 may make this effect smaller than one would expect.)

8. a. The tert-butyl group is electron-donating compared to H, which stabilizes the key

cationic intermediate in the para isomer compared to the meta isomer:

b. The ortho isomer is electronically stabilized in much the same way as the para isomer,
but the large size of the tert-butyl group impedes reactivity adjacent to it.

c. Many acetylating agents will serve the role as X; acetic anhydride is shown in the
scheme.

d. Any source of tert-butyl cation ((CH3)3COH/H+, (CH3)3CCl/AlCl3, etc.) will react with
benzene to give tert-butylbenzene: