2021 Fall Semester Mid-term Examination

For General Chemistry I

Date: Oct 20 (Wed), Time Limit: 19:00 ~ 22:00

NOTICE
 If you have a printer, print the papers and write the answers in the space of each question. If not,
prepare several A4-size papers to write only question # and the answers on it in the following
example. And for clarity, marking your answer is recommended. Please, print your Student ID in
the upper right corner of every page for both of them. (Handwriting only is acceptable and typing
is not.)
Example:

Professor Name Class Student I.D. Number Name

#1. (a)………
(b)……..
 If you have any questions during the period, please contact the TA of your class using the Zoom
chat channel to “Everyone” (the only possible choice). Proctors will make any announcements
relevant to all students via audio.
 While still in the video conference, submit your file to [Midterm Examination], an assignment on
Turnitin of your class. Do not leave the video conference until your TA is confirmed and tells you
that it is fine to leave.
** This paper consists of 14 sheets with 11 problems (page 13 - 14: Equation, constants & periodic table). Please check all
the page numbers before taking the exam. Please write down the unit of your answer when applicable. You will get 30%
deduction for a value that is missing its unit.

NOTICE: SCHEDULES on RETURN and CLAIM of the MARKED EXAM PAPER.

(채점 답안지 분배 및 이의신청 일정)
1. Period, Location, and Procedure
1) Return and Claim Period: Oct 25 (Mon 12:00~24:00)
2) Location: Each class of Turnitin site (online)
3) Procedure: If you have any claims on it, email them (Question# and reasons) to your TA.
(The claim is permitted only during the designated claim period. Keep that in mind! A solution file with answers for
the examination will be uploaded on the web.)
2. Final Confirmation
1) Period: Oct 28-29 (Thu – Fri)
2) Procedure: During this period, you can check final score of the examination on the website again.
(No additional corrections. If no change in your score after reasoning, the claims were not accepted.)
** For further information, please visit General Chemistry website at www.gencheminkaist.pe.kr

1
1. (total 8 pts)
Methane (CH4), xenon tetrafluoride (XeF4), and sulfur tetrachloride (SCl4) all have molecular
structures of the central atom bonded to four other atoms.

(a) Draw the Lewis diagrams of CH4, XeF4, and SCl4, and state their molecular geometries. (6 pts)

(Answer)

CH4: diagram 1 pt, geometry 1 pt

XeF4: diagram 1 pt, geometry 1 pt
SCl4: diagram 1 pt, geometry 1 pt

(b) Explain why these three molecules have different molecular geometries, although they all have a
similar chemical formula of AX4. (2 pts)

(Answer)
Though CH4, XeF4, and SCl4 all have four bonding pairs, they have the different number of lone pairs,
which give them different steric numbers. CH4 has 4 bonding pairs and 0 lone pair, and because all
four bonding pairs repel one another with equal strength, four hydrogen atoms lie at equal distance
from one another, giving CH4 the tetrahedral shape. XeF4 has 4 bonding pairs and 2 lone pairs. While
lone pairs affect the arrangement of other electron pairs, they are ignored when determining the
molecular geometry, and thus XeF4 has a molecular geometry of square planar. In a similar manner,
because SCl4 has 4 bonding pairs and 1 lone pair and a lone pair is not included in determining a
molecular geometry, SCl4 has a see-saw shape. full points for correct answer

2
2. (total 10 pts)
Boron trifluoride, BF3, is a highly reactive gas that condenses to a liquid at -100 oC.
(a) Draw the Lewis diagram of BF3 when this molecule follows the octet rule. Clearly mark the formal
charges. (3 pts)

(Answer)
Lewis structure +1pt, resonance form +1pt, formal charge +1pt

(b) Experimental evidence strongly suggests there are no double bonds in BF3. Draw the Lewis
diagram if BF3 does not follow the octet rule. (2 pts)
(Answer)

F B F

(c) Explain the three dimensional structure of BF3 using the valence bond theory. (3 pts)
(Answer) sp2 hybrid +1 pt, trigonal planar +1 pt, reasonable explanation +1
In the lecture slide,

(d) Although there are only single bonds in BF3, the length of the B-F bonds (1.30 Å) is shorter than
would be expected for common single bonds. What may lead to this shortness? (2 pts)
(Answer) Any reasonable descriptions, +2

3
This shortness may indicate stronger B-F pi-bonding (perpendicular to the molecular plane) in the
fluoride, although there are no strict double bonds. The ionic nature of the bonds may also strengthen
the B-F bond.

4
3. (total 10 pts)
The motion of an electron in a bond can be treated approximately as the motion in an one-dimensional
box. Consider the electrons in O2 and ozone (O3), and note that the lengths of the O-O and O=O bonds
are 1.48 and 1.21 Å, respectively.

(a) Calculate the energy of an electron in each of its three lowest allowed states if it is confined to
move in a one-dimensional box. (6 pts)

(Answer)
The allowed energies of a particle in an one-dimensional box are given by text equation 4.37

ℎ2 𝑛𝑛2
𝐸𝐸𝑛𝑛 =
8𝑚𝑚𝐿𝐿2

The particle in this case is an electron, so the value of m is known. The box length of O2 is 1.21 ×10-

10 O O O O O O
m and that of ozone with the resonance structures of is
(1.21+1.48) ×10-10 m. For n=1,2,3,

O2; E1=4.12*10-18 J, E2=16.5*10-18 J, E3=37.0*10-18 J

O3; E1=0.83*10-18 J, E2=3.33*10-18 J, E3=7.49*10-18 J

+1 pt for six Es

2 pt if rationale is correct

(b) Calculate the wavelength of light necessary to excite the electron from its ground state to the first
excited state. (4 pts)

(Answer)
The wavelength of the photon required to excite the electron from n=1 to n=2 is
ℎ𝑐𝑐
𝜆𝜆 = 𝐸𝐸 ; for O2, 1.61*10-8 m = 16.1 nm & for O3, 7.95*10-8 m = 79.5 nm.
2 −𝐸𝐸1

+2 pt for each

5
4. (total 6 pts)
An electron falls from n=5 state to n=3 state and then to n=1 state.
(a) Let’s define ν1 as the frequency of light emitted in transition from n=5 state to n=3 state, ν2 as the
frequency of light emitted in transition from n=3 state to n=1 state, and νtot as the frequency of the light
that would be emitted if it falls directly from n=5 to n=1 state. Find the relation between ν1, ν2, and νtot.
(3 pts)
(Answer)
The total energy emitted is equal to the sum of the energy emitted at the two transitions. This implies
hvtot= hv1+hv2
dividing by h gives vtot=v1+v2

(b) Find the relation between the respective wavelengths, λ1, λ2, and λtot. (3 pts)
(Answer)
to find the relation between the wavelengths we substitute frequencies by the c/λ. I.E
C/λtot=c/λ1+c/λ2
Dividing by c gives
1/λtot=1/λ1+1/λ2 rearranging gives
λtot=λ1λ2/(λ1+λ2)

6
5. (total 10 pts)
By photoelectron spectroscopy, three ionization energies were identified for electrons in Ne: 870.2,
48.4, and 21.6 eV. Answer the following questions.
(a) Draw an energy-level diagram for Ne, assign atomic orbitals for each energy level, and fill up the
electrons in the orbitals. (3 pt)

(Answer)

Diagram 1 pt

Orbital assignment 1 pt

Electron filling 1 pt

(b) Based on the Bohr theory, calculate the energy level of the lowest orbital for Ne: (2 pt)

En = -2.18×10-18 J (Z2/n2)

(Answer)
As Z = 10 and n = 1, E1 = -2.18×10-16 J 2 pts

(c) Estimate the effective Z (Zeff) that can match the Bohr theory with the experimental observation.
(3 pt)

(Answer)
The experimentally determined E1s = -870.2 eV ×1.60×10-19 J/eV = -1.39×10-16 J

(Zeff)2 = -1.39×10-16 J/-2.18×10-16 J×12 , Zeff = 8.00 3f pts

(d) Suppose Ne is excited by X-ray with energy of 1000 eV. Calculate the velocity of photoelectron
that was originally in the lowest orbital. (2 pt)

(Answer) As 870.2 eV = 1000 eV – 1/2meve2, ve = 6.76×106 m/s 2 pts

7
6. (total 6 pts)
Calculate the average distance (Å) of an electron from the nucleus in the
a) 1s orbital in a H atom
b) 2s orbital in a He+ atom
c) 2p orbital in a Be3+ atom

(Answer)
a) H atom

= = 0.7935 Å

b) He+ atom

= = 1.587 Å

c) Be3+ atom

= =0.66125 Å

2 pts each

8
7. (total 10 pts)
If an electron is removed from a fluorine molecule, an F2+ molecular ion forms.
(a) Give the molecular electron configurations for F2 and F2+. (3 pt)

(Answer)
F2 is a homonuclear diatomic molecule, which has 18 electrons of which 14 are valence electrons. The
he F2+ ion has lost a valence electron and so has 13. Based on the correlation diagram for F2, the
energetic order can be obtained like the following.

F2 (σg2s)2(σ*u2s)2(σg2p)2(πu2p)4(π*g2p)4

F2+ (σg2s)2(σ*u2s)2(σg2p)2(πu2p)4(π*g2p)3

(b) Give the bond order of each species. (2 pts)

(Answer)
The F2 molecule has two more bonding than antibonding electrons. Its order is 1; F2+ ion has three
more bonding than antibonding electrons. Its bonding order is 3/2.

(c) Predict which species should be paramagnetic. (2 pt)

(Answer)
The F2 molecule has zero unpaired electrons. Accordingly, F2 is diamagnetic. The F2+ ion has an odd
number of electrons. Because at least one electron (a π*g2p electron) is unpaired. So, F2+ ion is
paramagnetic.

(d) Predict which species has the greater bond dissociation energy. (3 pts)

(Answer)
The F2+ ion has a larger bond order and therefore requires more energy to dissociate than F2+ ion’s
case.

9
8. (total 10 pts)
The figure below shows the energy levels of OH molecular orbitals obtained by combining O and H
atomic orbitals. (Note: E2 orbitals are obtained only from O atomic orbitals and called non-bonding
molecular orbitals.)

(a) Properly draw the ground state electron configuration. Fill up the electrons of atomic orbitals, too.
(3 pts)

(Answer)

(b) Is the first ionization energy of OH less than that of H? Please explain the reason for your answer.
(2 pts)

(Answer)
No. Because the electrons in the HOMO of OH have a lower energy level than the 1s electrons of H,
and thus have higher ionization energy.

(c) What is the bond order of the ground state OH? (2 pts)

(Answer)
Bond order = (1/2) x (number of electrons in bonding MOs – number of electrons in antibonding

MOs) = 2/2 = 1

(d) Why do we call OH a “radical”? How does the MO diagram support this? (2 pts)

10
(Answer)
It has an unpaired electron in a non-bonding orbital.

(e) Is there a nodal plane between H and O in the molecular orbital corresponding to E3? (1 pts)

(Answer)
Yes.

11
9. (total 10 pts)
The following is a device that connects two containers containing gas A and gas B with a cock. Gas A
reacts with gas B to form gas C. The cock was opened and equilibrium was reached. (The temperature
is constant, all gases behave ideally, and the reaction proceeded completely. Ignore the volume of the
connection between two containers.)
2A(g) + B(g) → 2C(g)

(a) How many centimeters did the piston move? Write the length and direction of piston movement.
(5 pts)
(Answer)
2A + B → 2C
Before reaction 1.2atm*2L 1atm*1L
After reaction -2atm*L -1atm*L +2atm*L
0.4atm*L 2atm*L
Total: 2.4 atm*L
Pressure of inside and outside of the piston is same as 1 atm.
So, total volume is 2.4 L. The piston should come down 6 cm to meet the volume.
Answer) 6 cm, down
Fine with different methods
(b) What is the mole fraction of each gas? (3 pts)
(Answer)
A: 1/6, B: 0, C: 5/6

(c) The ratio of the molecular weights of gas A and B is 1:2. Find the ratio of the diffusion rates of A
and C. (2 pts)
(Answer)

12
 V𝐴𝐴 M
MC=(2MA+MB)/2, MA:MB:MC=1:2:2, = �M𝐶𝐶 = √2, V𝐴𝐴 = √2V𝐶𝐶
V𝐶𝐶 𝐴𝐴

13
10. (total 10 pts)

Formula Name M.W. a (bar•L2/mol2) b (L/mol)

(a) C2H5F Fluoroethane 48.06 8.17 0.07758
(b) CH3SH Methanethiol 48.11 8.911 0.06756
(c) C2H4O2 Methyl formate 60.05 11.54 0.08442
(d) CH3COOH Acetic acid 60.05 17.71 0.1065
(e) C2F4 Tetrafluoroethylene 100.02 6.954 0.08085
(f) C2H5Br Bromoethane 108.96 11.89 0.08406

For molecules (a)~(f), the chemical formula, the molecular weight, and the van der Waals constants
a’s and b’s are given in the above table. Which of the following is correct in predicting boiling points
in an increasing order? Choose an answer and give an explanation.

①a<b<c<d<e<f
②e<a<b<c<f<d
③b<a<e<f<c<d
④a<b<c<e<f<d
⑤d<f<c<b<a<e

(Answer)
② e < a < b < c < f < d is correct. +5 pts
From the van der Waals equation, the vapor pressure of real gases can be predicted. A higher “a” value
indicates greater attractive interactions between molecules and thus smaller vapor pressure. Then more
thermal energy is required for reaching 1 atm, i.e., boiling.
𝑛𝑛2
�P + a � (𝑉𝑉 − 𝑛𝑛𝑛𝑛) = 𝑛𝑛𝑛𝑛𝑛𝑛
𝑉𝑉 2
𝑅𝑅𝑅𝑅 𝑛𝑛
𝑃𝑃 = − 𝑎𝑎( )2
𝑉𝑉 𝑉𝑉
− 𝑏𝑏
𝑛𝑛
+5 pts

14
11. (total 10 pts)
The boiling point of HF, HCl, HBr and HI are 293K, 189K, 206K and 238K, respectively.
(a) Which type of intermolecular forces are present in the molecules HF, HCl, HBr, and HI? (4 pts)

(Answer)
HCl, HBr and HI: dipole-dipole and London forces
HF: hydrogen bonding, dipole-dipole, and London forces

(b) Looking at the trend of boiling points of HCl, HBr and HI, which intermolecular force is
predominant among these molecules? (4 pts)

(Answer)
Electronegativity decreases from Cl to I, so the dipole moment decreases from HCl to HI. As the
boiling point is increasing from HCl to HI, it means London forces are predominant.
London force is directly proportional to the number of electrons in a molecule.

(c) Why is the boiling point of HF the highest? (2 pts)

(Answer)
F has the highest electronegativity. As a result, HF has the highest dipole moment and also has
hydrogen bonding. Therefore, HF shows the highest boiling point.

15
Physical Constants

Avogadro’s number NA = 6.02214179 ⅹ 1023 mol-1

Bohr radius a0 = 0.52917720859 Å = 5.2917720859ⅹ10-11 m
Boltzmann’s constant KB = 1.3806504 ⅹ 10-23 J K-1
Electronic charge e = 1.602176487 ⅹ 10-19 C
Faraday constant F = 96485.3399 C mol-1
Masses of fundamental particles:
Electron me = 9.10938215 ⅹ 10-31 kg
Proton mP = 1.672621637 ⅹ 10-27 kg
Neutron mn= 1.674927211 ⅹ 10-27 kg
Permittivity of vacuum εo = 8.854187817 ⅹ 10-12 C-2 J-1 m-1
Planck’s constant h = 6.62606896 ⅹ 10-34 J s
Ratio of proton mass to electron mass mP / me = 1836.15267247
Speed of light in a vacuum c = 2.99792458 ⅹ 108 m s-1 (exactly)
Standard acceleration of terrestrial gravity g = 9.80665 m s-2 (exactly)
R = 8.314472 J mol-1 K-1
Universal gas constant
= 0.0820574 L atm mol-1 K-1
Values are taken from the 2006 CODATA recommended values,
as listed by the National Institute of Standards and Technology.

Conversion factors

Ångström 1 Å= 10-10 m
Atomic mass unit 1 u = 1.660538782 ⅹ 10-27 kg
1 u = 1.492417830 ⅹ 10-10 J = 931.494028 MeV (energy equivalent form E = mc2)
Calorie 1 cal = 4.184 J (exactly)
Electron volt 1 eV = 1.602177 ⅹ 10-19 J = 96.485335 kJ mol-1
Foot 1 ft = 12 in = 0.3048 m (exactly)
Gallon (U. S.) 1 gallon = 4 quarts = 3.785412 L (exactly)
Liter 1 L = 10-3 m-3 = 103 cm3 (exactly)
Liter-atmosphere 1 L atm = 101.325 J (exactly)
Metric ton 1 t = 1000 kg (exactly)
Pound 1 lb = 16 oz = 0.4539237 kg (exactly)
Rydberg 1 Ry = 2.17987197 x 10-18J = 1312.7136 kJ mol-1 = 13.60569193 eV
Standard atmosphere 1 atm = 1.01325 x 105 Pa = 1.01325 x 105 kg m-1 s-2 (exactly)
Torr 1 torr = 133.3224 Pa

16
17
 2021 Fall Semester Final Examination
For General Chemistry I

Date: Dec 15 (Wed), Time Limit: 19:00 ~ 22:00

NOTICE
 If you have a printer, print the papers and write the answers in the space of each question. If not,
prepare several A4-size papers to write only question # and the answers on it in the following
example. And for clarity, marking your answer is recommended. Please, print your Student ID in
the upper right corner of every page for both of them. (Handwriting only is acceptable and typing
is not.)
Example:

Professor Name Class Student I.D. Number Name

#1. (a)………
(b)……..
 If you have any questions during the period, please contact the TA of your class using the Zoom
chat channel to “Everyone” (the only possible choice). Proctors will make any announcements
relevant to all students via audio.
 While still in the video conference, submit your file to [Final Examination], an assignment on
Turnitin of your class. Do not leave the video conference until your TA is confirmed and tells you
that it is fine to leave.
** This paper consists of 13 sheets with 10 problems (page 12-13: Equation, constants & periodic table). Please check all
page numbers before taking the exam. Please write down the unit of your answer when applicable. You will get 30%
deduction for a value that is missing its unit.

NOTICE: SCHEDULES on RETURN and CLAIM of the MARKED EXAM PAPER

(채점 답안지 분배 및 이의신청 일정)
1. Period, Location, and Procedure
1) Return and Claim Period: Dec 18 (Sat, 12:00 ~ 24:00)
2) Location: Each class of Turnitin site (online)
3) Procedure: If you have any claims on it, email them (Question# and reasons) to your designated TA.
(The claim is permitted only during the designated claim period. Keep that in mind! A solution file with answers for
the examination will be uploaded on the web.)
2. Final Confirmation
1) Period: Dec 20 (Mon, 12:00 ~ 24:00)
2) Procedure: During this period, you can check final score of the examination on the website again.
(No additional corrections. If no change in your score after reasoning, the claims were not accepted.)
** For further information, please visit General Chemistry website at www.gencheminkaist.pe.kr

1
1. (total 10 pts)
A mixture of 1.78 kg of water and 262 g of ice at 0°C is in a reversible process, brought to a final
equilibrium state where the water-to-ice mass ratio is 1:1 at 0°C. (∆Hfus (H2O) = 6.007 kJ/mol, Molar
mass of H2O: 18.02 g/mol)
(a) Calculate the entropy change of the system during this process.

(Answer) (5 pts)

Mass of ice-water mixture = (Mass of water) + (Mass of ice) = (1.78 kg) + (0.262 kg) = 2.04 kg

If eventually the ice and water have the same mass, then the final state will have 1.02 kg (2.04 kg/2)
of each.
The mass of the water that changed into ice, ∆m, will be the difference of initial mass of water mi and
final mass of water mf.
∆m = mi - mf = 1.78 kg – 1.02 kg = 0.76 kg
760 g / 18.02 g/mol = 42.18 mol
The change in entropy at 0° C
n∆H𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓 n∆H𝑓𝑓𝑓𝑓𝑓𝑓 (42.18 𝑚𝑚𝑚𝑚𝑚𝑚)(6007 𝐽𝐽 𝑚𝑚𝑚𝑚𝑚𝑚 −1 )
∆S = =− =− = − 927.6 𝐽𝐽 𝐾𝐾 −1
T T 273.15 𝐾𝐾

(b) The system is then returned to the first equilibrium state, but in an irreversible way. The system is
heated by using a Bunsen burner. Heat of 3.04 x 105 J is used. Calculate the entropy change of the
system during this process with proper explanation.

(Answer) (5 pts)

The entropy S of a system is a state function and depends only on the state of the system and not how
it reached that condition.
Now the system is returned to the first equilibrium state, but in an irreversible way. Thus, the change
in entropy ΔS of the system during this process is equal to the negative of previous case.
So, ΔS = -(- 927.6 J/K) = 927.6 J/K

2
2. (total 10 pts)
Over what range of temperature is each of the following processes spontaneous? Assume that all gases
are at a pressure of 1 atm. Use the following table, and assume that the enthalpies and entropies are
independent upon the temperature.
∆Hfo So ∆Hfo So
Substance Substance
(kJ mol-1) (J K-1 mol-1) (kJ mol-1) (J K-1 mol-1)
Fe(s) 27.28 CO(g) -110.52 197.56
FeO(s) -266.27 57.49 COCl2(g) -218.8 283.53
Fe2O3(s) -824.2 87.40 O2(g) 205.03
C(s) 5.74 Cl2(g) 222.96
(a) The rusting of iron, a complex reaction that can be approximated as
4 Fe(s) + 3 O2 (g) → 2 Fe2O3(s)
(Answer)
∆Hfo = 2 x (-824.2) = -1648.4 kJ mol-1
∆So = 2 x (87.40) – 4 x (27.28) – 3 x (205.03) = -549.41 J K-1 mol-1
T = ∆Hfo / ∆So = -1648.4x103 / -549.41 = 3000 K +3 pts
The reaction is spontaneous below 3000 K. below, +1 pt

(b) The preparation of the poisonous gas phosgene: CO(g) + Cl2(g) → COCl2(g)
(Answer)
∆Hfo = (-218.8) – (-110.52) = -108.3 kJ mol-1
∆So = (283.53) – (222.96) – (197.56) = -136.99 J K-1 mol-1
T = ∆Hfo / ∆So = -108.3x103 / -136.99 = 790 K +2 pts
The reaction is spontaneous below 790 K. below, +1 pt

(c) The reduction of iron(II) oxide (wüstite) by coke (carbon), a step in the production of iron in a
blast furnace: FeO(s) + C(s, gr) → Fe(s) + CO(g)
(Answer)
∆Hfo = (-110.52) – (-266.27) = 155.75 kJ mol-1
∆So = (27.28) + (197.56) – (57.49) – (5.74) = 161.61 J K-1 mol-1
T = ∆Hfo / ∆So = 155.75x103 / 161.61 = 960 K +2 pts
The reaction is spontaneous above 960 K. above, +1 pt

3
3. (total 10 pts)
A student claims that the process of recycling aluminum (initially at 298.15 K) by melting the metal
to remove impurities requires less energy than the process of extracting Al from Al2 O3 as expressed
3
in the following equation: Al2 O3 (𝑠𝑠) → 2 Al(𝑠𝑠) + 2 O2 (𝑔𝑔). The melting point of Al is 933.47 K, the

molar heat capacity of Al is 24.20 J mol−1 K−1 , and the enthalpy of fusion of Al is
10.71 kJ mol−1. The standard enthalpy of formation of Al2 O3 is −1675.7 kJ mol−1. Calculate the
required energies of each process and determine if the student’s claim is true.

Recycling (Melting): (4 pts)

𝑛𝑛: moles of Al, 𝑐𝑐m : molar heat capacity of Al, ∆𝐻𝐻fus °: enthalpy of fusion of Al, 𝑇𝑇: temperature

The heat required for the process of melting the Al is the sum of the heat required to raise the
temperature to the melting point of 933.47 K from 298.15 K and the heat required to melt the Al.

𝑛𝑛𝑐𝑐m ∆𝑇𝑇 + 𝑛𝑛∆𝐻𝐻fus °

= 𝑛𝑛(24.20 J mol−1 K −1 )(933.47 K − 298.15 K) + 𝑛𝑛(10.71 × 103 J mol−1 )
= (2.608 × 104 J mol−1 )𝑛𝑛

Thus, 2.608 × 104 J required per mole of Al.

Extracting: (4 pts)

The given reaction of extracting Al from Al2 O3 is the reverse of the reaction of formation of Al2 O3 .
Therefore, the standard enthalpy of reaction for the reaction of extracting Al from Al2 O3 is
1675.7 kJ mol−1 .

1 mol rxn
1675.7 × 103 J mol−1 × × 𝑛𝑛 = (8.3785 × 105 J mol−1 )𝑛𝑛
2 mol Al

Thus, 8.3785 × 105 J required per mole of Al.

8.3785 × 105 J mol−1 > 2.608 × 104 J mol−1

(2 pts) ∴ TRUE

4
4. (total 12 pts)
The following cycle consists of two isobaric and two isochoric processes. The cycle starts at point 1
where P1 = 2 atm, V1 = 20 L. The volume at point 2 is then 60 L and the pressure at point 3 is 1 atm.
The cycle works with 1 mole of monoatomic gas.
(a) Calculate the work done on the gas during the 12, 23, 34, and 41 process in joules.
(b) Calculate the total work done by one cycle in joules.
(c) At what point does the gas reach a maximum temperature and what is that temperature?
(d) Calculate the entropy change of the system when the gas goes from state 1 to state 3.

A) Process 1-2 is an isobaric process. W = -PΔV = -40L * 2 atm = -80atm*L = - 8.106 kJ.
Process 2-3 is an isochoric process => no work. Process 3-4 is an isobaric process. W = W = -
PΔV = +40L * 1 atm = 40atm*L = + 4.053 kJ. Process 4-1 is an isochoric process => no
work. (4 pts; 1pt each)

B) Total Work: = W12 + W23 + W34 + W41 = -4.053 kJ (2pt)

C) At 1: T1=P1*V1/(n*R) = 487.4 K At 2: T2=P2*V2/(n*R) = 1462.4 K. At 3: T3=P3*V3/(n*R) =

731.2 K. At 4: T4=P4*V4/(n*R) = 243.7 K. So we reach a maximum temperature at point 2
with 1462.4 K. (3 pts)

D) We can either choose Path 1-2-3 or Path 1-4-3, since entropy is a function of state. For 1-2-3:
𝑇𝑇2 𝑐𝑐 𝑇𝑇3
𝑝𝑝 𝑐𝑐𝑣𝑣 𝑇𝑇2 𝑇𝑇3 5𝑅𝑅 𝑇𝑇2 3𝑅𝑅 𝑇𝑇3
∆𝑆𝑆 = � 𝑑𝑑𝑑𝑑 + � 𝑑𝑑𝑑𝑑 = 𝑐𝑐𝑝𝑝 × 𝑙𝑙𝑙𝑙 + 𝑐𝑐𝑣𝑣 𝑙𝑙𝑙𝑙 = × 𝑙𝑙𝑙𝑙 + × 𝑙𝑙𝑙𝑙
𝑇𝑇1 𝑇𝑇 𝑇𝑇2 𝑇𝑇 𝑇𝑇1 𝑇𝑇2 2 𝑇𝑇1 2 𝑇𝑇2
5 3
= 𝑅𝑅 � × 1.0986 + × (−0.6931)� = 𝑅𝑅 × 1.706 = 14.2 𝐽𝐽 𝐾𝐾 −1
2 2
(3 pts)

5
5. (total 10 pts)
The water–gas shift reaction is important in several chemical processes, such as the production of H2
for fuel cells. This reaction can be written as follows:
H2 (g) + CO2 (g) ⇄ H2O (g) + CO (g)
The equilibrium constant K = 0.106 at 700 K. If a mixture of gases that initially contains 0.0150 M H2
and 0.0150 M CO2 is allowed to equilibrate at 700 K, what are the final concentrations of all substances
present?

(Answer)

Reaction H2 (g) + CO2 (g) ⇌ H2O (g) + CO (g)

Initial 0.0150 0.0150 0 0
Change -x -x +x +x
Equilibrium 0.0150 - x 0.0150 - x x x

We can now use the equilibrium equation and the given K to solve for x:
[𝐻𝐻2 𝑂𝑂][𝐶𝐶𝐶𝐶] (𝑥𝑥)(𝑥𝑥) 𝑥𝑥 2
𝐾𝐾 = = = = 0.106
[𝐻𝐻2 ][𝐶𝐶𝐶𝐶2 ] (0.0150 − 𝑥𝑥)(0.0150 − 𝑥𝑥) (0.0150 − 𝑥𝑥)2
𝑥𝑥 2
= 0.106
(0.0150 − 𝑥𝑥)2
𝑥𝑥
= 0.1060.5 = 0.326
(0.0150 − 𝑥𝑥)
x = 0.00369 M (2 pts)

The equilibrium concentrations of all species in the reaction mixture are as follows:
[H2]e = (0.0150 − x) = (0.0150 − 0.00369) = 0.0113 M (2 pts)
[CO2]e = (0.0150 − x) = (0.0150 − 0.00369) = 0.0113 M (2 pts)
[H2O]e = x = 0.00369 M (2 pts)
[CO]e = x = 0.00369 M (2 pts)
We can check our work by inserting the calculated values back into the equilibrium constant expression:
[𝐻𝐻2 𝑂𝑂][𝐶𝐶𝐶𝐶] (0.00369)2
𝐾𝐾 = = = 0.107
[𝐻𝐻2 ][𝐶𝐶𝐶𝐶2 ] (0.0113)2

6
6. (total 6 pts)
Consider a weak acid, HA, with pKa = 5.20. You start with 100.0 mL of a buffer solution in which [A-]
= 0.40 M and [HA] = 0.60 M. You add 100 mL of 0.10 M NaOH solution. What is the change in pH
caused by addition of NaOH?
(Answer)
Initial pH:
[𝐻𝐻𝐻𝐻] 0.60
pH = p𝐾𝐾𝑎𝑎 − 𝑙𝑙𝑙𝑙𝑙𝑙10 � − � = 5.2 − 𝑙𝑙𝑙𝑙𝑙𝑙10 � � = 5.02
[𝐴𝐴 ] 0.40
(3 pts)
When OH- is added:
[HA] → 0.30 M, [OH-] → 0.05 M, [A-] → 0.20 M
Reaction HA (aq) + OH- (aq) ⇄ A-(aq) + H2O (l)
Initial 0.30 0.050 0.20
Change - 0.050 - 0.050 + 0.050
Equilibrium 0.25 0 0.25

[𝐻𝐻𝐻𝐻] 0.25
pH = p𝐾𝐾𝑎𝑎 − 𝑙𝑙𝑙𝑙𝑙𝑙10 � − � = 5.2 − 𝑙𝑙𝑙𝑙𝑙𝑙10 � � = 5.20
[𝐴𝐴 ] 0.25
Change in pH = + 0.18 (3 pts)

7
7. (total 10 pts)
In a saturated solution of MgF2 at 18oC, the concentration of Mg2+ is 1.21 x 10-3 M. The equilibrium
is represented by the equation below.
MgF2 (s) ⇄ Mg2+ (aq) + 2 F-(aq)

(a) Write the expression for the solubility product constant, Ksp, and calculate its value at 18oC.
(Answer) (4 pts)
Ksp = [Mg2+] [F-]2
[Mg2+] = 1.21 x 10-3 M
[F-] = 2 x 1.21 x 10-3 = 2.42 x 10-3 M
Ksp = (1.21 x 10-3)(2.42 x 10-3)2 = 7.09 x 10-9
(b) Calculate the equilibrium concentration of Mg2+ in 1.00 liter of saturated MgF2 solution at 18oC to
which 0.100 mole of solid KF has been added. The KF dissolves completely. Assume the volume
change is negligible.
0.100 𝑚𝑚𝑚𝑚𝑚𝑚
[𝐹𝐹 − ] = = 0.100 𝑀𝑀
1.00 L
Compared to this value, initial concentrations of Mg2+ and F- are negligible and can be set to 0.
Reaction MgF2 (s) ⇄ Mg2+ (aq) + 2 F- (aq)
Initial 0 0.100
Change +x +2x
Equilibrium x 0.100 + 2x
Ksp = [Mg2+][F-]2
7.09 x 10-9 = (x)(0.100 + 2x)2
7.09 x 10-9 = (x)(0.100)2 since 2x is negligibly small.
x = 7.09 x 10-7 M = [Mg2+] (3 pts)

(c) Predict whether a precipitate of MgF2 will form when 100.0 mL of a 3.00 x 10-3 M Mg(NO3)2
solution is mixed with 200.0 mL of a 2.00 x 10-3 M NaF solution at 18oC.
(Answer) (3 pts)
Total solution volume = 100.0 mL + 200.0 mL = 300.0 mL = 0.300 L
[Mg2+] = (3.00 x 10-3 M)(0.100 L) / (0.300 L) = 1.00 x 10-3 M
[F-] = (2.00 x 10-3 M)(0.200 L) / (0.300 L) = 1.33 x 10-3 M
Q = [Mg2+][F-]2 = (1x 10-3)(1.33 x 10-3)2 = 1.78 x 10-9 < Ksp = 7.09 x 10-9
Since Q < Ksp, a precipitate of MgF2 will not be formed.

8
8. (total 12 pts)
The solubility products for a series of iodides are
CuI Ksp = 1 x 10-12
AgI Ksp = 8.3 x 10-17
PbI2 Ksp = 7.1 x 10-9
BiI3 Ksp = 8.1 x 10-19
List these four compounds in order of decreasing molar solubility in
(a) water.

(b) 0.20 M NaI.

(c) 0.020 M solution of the solute cation.

Answer) (4 pts each)

9
9. (total 10 pts)
Consider the following galvanic cell:

Ag++e-→Ag E0=0.80V
Pb2++2e-→Pb E0=-0.13V
Calculate the Ksp value for Ag2SO4(s). To obtain silver ions in the right compartment (the cathode
compartment), excess solid Ag2SO4 was added and some of the salt dissolved.
(Answer)

(6 pts)

(4 pts)

10
10. (total 10 pts)
The following reduction potentials are measured at pH 0:
1
𝐵𝐵𝐵𝐵𝐵𝐵3− (𝑎𝑎𝑎𝑎) + 6𝐻𝐻3 𝑂𝑂+ (𝑎𝑎𝑎𝑎) + 5𝑒𝑒 − → 2 𝐵𝐵𝐵𝐵2 (𝑙𝑙) + 9𝐻𝐻2 𝑂𝑂(𝑙𝑙) 𝐸𝐸 0 = 1.52 𝑉𝑉

𝐵𝐵𝐵𝐵2 (𝑙𝑙) + 2𝑒𝑒 − → 2𝐵𝐵𝐵𝐵 − (𝑎𝑎𝑎𝑎) 𝐸𝐸 0 = 1.065 𝑉𝑉

(a) Will bromine (Br2 (l)) disproportionate to BrO3− (aq) and Br − (aq) spontaneously in acidic
solution? & why?

(b) Which is the stronger reducing agent at pH 0: 𝐵𝐵𝐵𝐵2 (𝑙𝑙) 𝑜𝑜𝑜𝑜 𝐵𝐵𝐵𝐵 −? & why?

Answer:

(a) Ecell calculation: 3 pts; phrase ‘no disproportionation’: 2pts

(b) Answer: 3pts, reason: 2pts

11
Physical Constants

Avogadro’s number NA = 6.02214179 ⅹ 1023 mol-1

Bohr radius a0 = 0.52917720859 Å = 5.2917720859ⅹ10-11 m
Boltzmann’s constant KB = 1.3806504 ⅹ 10-23 J K-1
Electronic charge e = 1.602176487 ⅹ 10-19 C
Faraday constant F = 96485.3399 C mol-1
Masses of fundamental particles:
Electron me = 9.10938215 ⅹ 10-31 kg
Proton mP = 1.672621637 ⅹ 10-27 kg
Neutron mn= 1.674927211 ⅹ 10-27 kg
Permittivity of vacuum εo = 8.854187817 ⅹ 10-12 C-2 J-1 m-1
Planck’s constant h = 6.62606896 ⅹ 10-34 J s
Ratio of proton mass to electron mass mP / me = 1836.15267247
Speed of light in a vacuum c = 2.99792458 ⅹ 108 m s-1 (exactly)
Standard acceleration of terrestrial gravity g = 9.80665 m s-2 (exactly)
R = 8.314472 J mol-1 K-1
Universal gas constant
= 0.0820574 L atm mol-1 K-1
Values are taken from the 2006 CODATA recommended values,
as listed by the National Institute of Standards and Technology.

Conversion factors

Ångström 1 Å= 10-10 m
Atomic mass unit 1 u = 1.660538782 ⅹ 10-27 kg
1 u = 1.492417830 ⅹ 10-10 J = 931.494028 MeV (energy equivalent form E = mc2)
Calorie 1 cal = 4.184 J (exactly)
Electron volt 1 eV = 1.602177 ⅹ 10-19 J = 96.485335 kJ mol-1
Foot 1 ft = 12 in = 0.3048 m (exactly)
Gallon (U. S.) 1 gallon = 4 quarts = 3.785412 L (exactly)
Liter 1 L = 10-3 m-3 = 103 cm3 (exactly)
Liter-atmosphere 1 L atm = 101.325 J (exactly)
Metric ton 1 t = 1000 kg (exactly)
Pound 1 lb = 16 oz = 0.4539237 kg (exactly)
Rydberg 1 Ry = 2.17987197 x 10-18J = 1312.7136 kJ mol-1 = 13.60569193 eV
Standard atmosphere 1 atm = 1.01325 x 105 Pa = 1.01325 x 105 kg m-1 s-2 (exactly)
Torr 1 torr = 133.3224 Pa

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