CHEMISTRY 2090

PRELIM I

October 8, 2015

Answers

1. (8 points) An unknown atom Z forms multiple chlorides with the generic formula Zx Cly . One
such compound is analyzed and found to contain 77.5% Cl by mass; a second, 85.1% Cl by
mass. Show that these compounds conform to Daltons law of multiple proportions.

Other than the substitution of Z where it used to say P, this was a clicker question; the answer
given in class is shown below.

For those of you with answers for the ratio of 10:6, 6:10, 3:2, 2:3 or anything
similar, if you did not receive full credit you might wish to submit your exam
for reconsideration.

2. (a) (5 points) If 7.45 1021 atoms of an unknown element X has mass 1.10 g, what is the
element X?

One mole of atoms contains 6.02 1023 atoms; so our sample of 7.45 1021 atoms represents
7.45 1021
= 1.238 102 moles of atoms, with mass 1.10 g. One mole therefore has mass
6.02 1023
1.10 g
= 88.9 g/mole. Suggesting the atom is Y.
1.238 102 mole

(b) (5 points) Radio signals sent from the first NASA flight to Jupiter, in the late 1970s,
were transmitted at a frequency of 8.34 109 s1 . The receiving antenna on earth was
capable of detecting 4.11 1021 watts (1 W = 1 J/s = 1 kg-m2 /s3 ). What was the
minimum number of photons/second which were required for a signal to register at the
antenna?

Energy/photon is h = (6.626 1034 Js)(8.34 109 /s) = 55.26 1025 = 5.526 1024
J/photon.
4.11 1021 J/s
So the antenna requires an input of
= 744 photons/s.
5.526 1024 J/photon

3. (a) (4 points) An electron is found to have a velocity such that its wavelength, , is equal to
the distance it travels in one second. What is its velocity?

We are told that = v 1 s. We also know that the DeBroglie wavelength is given by
h
h
h
=
; we can combine what we know to give v 1 s =
. Rearranging, we
=
p
me v
me v
h
6.626 1034 Js
find v 2 1 s =
=
; cancelling common units (remember that the J
me
9.109 1031 kg
is a kg-m2 /s2 !) leads to v 2 = 7.274 104 m2 /s2 . After taking the square root, we find
v = .02697 m. Call it 2.7 cm.

(b) (6 points) An intense beam of green light shines on a copper metal surface whose threshold
energy for the photoelectron effect is 0.753 aJ.
i. What is observed?
hc
Nothing. The threshold energy of 0.753 aJ/photon (E = ) corresponds to a photon

wavelength of
=

(6.626 1034 Js)(2.998 108 m/s)

hc
=
= 26.38 108 m = 264 nm
E
0.753 1018 J

264 nm is found in the ultravioletwhere green light is at longer wavelengths (500-600

nm), at lower energy.
ii. The intensity of the beam is doubled. What will be observed?
Still nothing. Output of photoelectrons requires higher energy photons, not more low
energy photons

iii. The green light of part (i) is replaced with an equally intense beam (same number
of photons/second) of red light. What will be observed?
Still nothing. Output of photoelectrons requires higher energy photons; red photons
carry less energy/photon than is found in green photons.

4. (a) (8 points) Nitric acid is produced commercially by the Ostwald process, whose first step
involves the reaction of ammonia (NH3 ) with oxygen (O2 ) via
4 NH3 (g) + 5 O2 (g) 4 NO (g) + 6 H2 O (g)
Assume the reaction described above is carried out in the apparatus shown below; all
measurements of pressure are made at T = 137 C.

Flask A contains 2.00 ` of NH3 at 0.500 atm; Flask B contains 1.00 ` of O2 at 1.50 atm.
The valve is opened and the reaction proceeds as the gases mix. What is the partial
pressure of NO produced, if the final container volume is 3.00 ` and we assume 100%
yield in the reaction as written?

The ideal gas law PV = nRT tells us that at fixed T, the product PV is proportional to the
number of moles. We could calculate n directly but it is less work to just find PV.
Flask A contains 1.00 `-atm of NH3 ; B contains 1.50 `-atm of O2 .
4 moles of NH3 react with 5 moles of O2 ; so the NH3 is limiting, and we use up all the NH3
5
(1.00 `-atm) and as much of the O2 , or 1.25 `-atm of O2 . Producing 1.00 `-atm of NO
4
and 1.50 `-atm of H2 O.
1
1
1
atm of O2 .
Final volume is 3 liters; so we have atmosphere of NO; atm of water, and
3
2
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(b) (8 points) Even in small quantities nicotine as found in tobacco is addictive. In large
quantities, it is a deadly poison. Find the empirical formula of nicotine (that is, x, y and
z for Cx Hy Nz ) if upon combustion of 4.40 mg of nicotine one collects 11.9 mg of CO2
and 3.41 mg of H2 O.

5. (10 points) 10.0 grams of a mixture of Ca(ClO)2 and Ca(ClO3 )2 are placed in 10.0 ` vessel
and heated to 700 C where the two compounds decompose via
Ca(ClO)2 (s) CaCl2 (s) + O2 (g)
and
Ca(ClO3 )2 (s) CaCl2 (s) + 3O2 (g)
The final pressure inside the vessel at T = 700 C is 0.91 atm. What is the mass of each
compound in the orginal mixture?

6. (a) (5 points) No object can travel faster than the speed of light, c; so the uncertainty in the
velocity, v can never be greater than 3 108 m/s. What is the minimum uncertainty,
x, in the position of an electron, if we know only that its velocity is less than c?

For those of you who left out me from the expression, and simply wrote
h
; (or if you plugged in the value of
something that looks like cx
4
c = v) you should have received 3 points in partial credit. If you didnt
please submit for a regrade. With our apologies.
(b) (5 points) An atom is observed to emit light at 100. nm, 125. nm, and 500. nm. Theory
predicts that only the ground state and two excited states are involved. In aJ, how far
above the ground state are the excited states?

A small amount of partial credit was given for calculating the energies of
transition. More was provided for the energy level diagram showing the
relationship between the states, and why there were three transitions with
only two excited states.
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7. (a) (7 points) The element arsenic (As) forms an oxide with formula Asx Oy which can be
studied as a gas. Under the same conditions of temperature (T ) and pressure (P ) it
is found that (i) the density of the gaseous Asx Oy is 12.4 times the density of gaseous
O2 , and that (ii) six volumes of gaseous hydrogen H2 react with one volume of gaseous
Asx Oy to form elemental arsenic and water.
i. The formula of the gaseous Asx Oy (i.e. identify as best you can x and y):
If the density of our unknown gas is 12.4 times that of O2 (with molecular weight 32.0)
then its molecular weight must be (12.4 0.1) 32.0 = 397 3 g/mole.
We also have the result Asx Oy + 6 H2 x As + y H2 O. The ratio of volumes is
the same as the ratio of moles of reactants, therefore y = 6 so as to keep balance of the
hydrogen atoms.
The atomic mass of As is 74.9; that of O, 16.0. The only combination of x and y = 6 that
comes close is As4 O6 with mass 395.6which is within the uncertainty bounds 397 3.

ii. Is this an empirical or molecular formula? (Explain your answer).

This is molecular. The density measures the mass of the units as they exist in the gas
phase, as we know that the number of gas units is identical to the number of O2 units
as the pressure and volume are identical to that of the oxygen
(b) (4 points) You have two closed containers as shown below; one contains gas X, the
second, gas Y . The two gases behave as ideal gases and are at the same temperature, T .
The molecular mass of Y is double that of X. The density of gas Y , in g/`, is half that
of X. Find the ratio of the pressure of X to the pressure of Y .

Gas Y has double the molecular mass of gas X. Container Y has half the density in g/liter
of container X. As each unit of gas Y has double the mass, there must be one-quarter as
many molecules of gas Y in container Y as there are or molecules of X in container X. As
the pressure is proportional to the number of molecules (for fixed temperature and identical
volume), the pressure in Y is one-quarter that in X. (The same result holds even if you dont
assume identical volumes, as the density is measured per liter; so the molecule density in any
specified volume in Y is also one-quarter the density in the same volume in X.)

8. (a) (4 points) How many electrons can have the sets of quantum numbers indicated below?
i. n = 3, m = 1
We are asked how many electrons can have the four quantum
numbers {n = 3, `, m = 1, ms }. There are three possible ` values for n = 3; that is,
` = 0, 1, or 2. For m = 1 we are limited to only ` = 1 or ` = 2. Each of the two orbitals
1
{3, 2, 1, ms } or {3, 1, 1, ms } can house two electrons, with spin ms = Four electrons
2
can have these quantum numbers.
1
ii. n = 2, ms =
Following the logic above, we seek allowed orbitals with quantum
2
1
numbers {n = 2, `, m, ms = }. ` can take on values ` = 0, with m = 0; or ` = 1,
2
with m = 1, 0 or m = 1. There are four possible orbitals, and four possible electrons
with the specified quantum numbers.
iii. n = 2, ` = 2
There are no possible orbitals; ` = 2 requires n 3.
iv. n = 4, ` = 2, m = 2

These quantum numbers describe one specific orbital; it can

1
house two electrons, with ms = .
2

(b) (4 points) Below are shown pictures of 2 for two H-atom orbitals; white areas correspond
to low probabilities, and black to high probabilites Which values of n and ` do these
orbitals represent? (Put your answers on the lines below the illustrations.)

4d

4p

(c) (2 points) Consider the orbitals listed below. Enter the total number of nodes, the
number of radial nodes and the number of angular nodes found, in each in the appropriate
columns.
orbital
all nodes
radial nodes
angular nodes
3s

2 total nodes

2 radial nodes

0 angular nodes

6f

5 total nodes

2 radial nodes

3 angular nodes

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(d) (3 points) Below are drawn a number of possible electronic configurations for the 8
electrons found in an oxygen atom (O). Electrons are drawn as arrows, whose direction
indicates the value of the spin quantum number ms . For each describe on the blank line
at right whether the configuration is excited if it represents a possible excited state
of the oxygen atom; ground if it represents the ground state, or forbidden if the
configuration cannot exist.

9. (a) (5 points) A series of emission lines are found in the spectrum of the one-electron atom
He1+ corresponding to transitions starting from the n = 6 electronic state. What are the
longest and shortest values of which can be observed in this series of lines?

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(b) (3 points) In the spectrum of the H atom, there is a blue line observed at 434.0 nm
corresponding to the emission of light as an excited H atom relaxes between the ni = 5
and nf = 2. The same line is observed in the He+ spectrum. For which pair of energy
levels ni and nf does the 434.0 nm line appear in He+ ?
Z2
in the one-electron atom with nuclear charge Z.
n2
So to get transitions at the same energy, we need to simply keep the ratio Z/n fixed; that is,
if we double Z in going from H to He+ , we also need to double n. So the same line at 434.0
nm is found in He+ for ni = 10 and nf = 4.

The energies of the various levels vary as

(c) (4 points) You are provided with He in a doubly excited state corresponding to an
electronic configuration 5s2 . The doubly-excited He atom emits a photon at 0 when it
undergoes the transition 5s2 1s1 5s1 . Would you expect 0 to be larger, smaller, or
the same as 1 observed for the transition from the singly excited state 1s1 5s1 1s2 ?
(You should not try to be quantitative; but, instead, describe how Zeff varies for the
various electrons in the different states.)
For the transition 1s1 5s1 1s2 we need to consider the energies of the electron undergoing
the transition, in the excited and ground state. In the excited state, it should be approximately hydrogen-like with Zeff 1 because the much closer 1s electron is very effective at
shielding the nuclear charge of one proton; the energy of the electron in the 5s orbital should
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be approximately 2.18 aJ( 2 ) 0.09 aJ. In the ground state, as we said in class, the
5
ionization energy of the He atom is about 3.9 aJ; or, if you prefer; Zeff 1.35 because each
of the 1s electrons partially shields the other, and therefore the transition energy should be
the difference between the energies of the two states: about 4 aJ (Im being loose as all we
really need are rough estimates!).
For the transition 5s2 1s1 5s1 one electron is making the same transition; but in a very
different background. In the doubly-excited state, it should be approximately hydrogen-like
with Zeff > 1 because the two 5s electrons partially shield one another; for purposed of
argument Ill choose Zeff = 2, the worst case, where there is no shielding; it wont really
matter, and then the energy of either electron in the 5s orbital should be approximately
22
2.18 aJ( 2 ) 0.35 aJ. In the 1s orbital, the electron sees effectively the full nuclear
5
charge Zeff 2 because the 5s electron is ineffective at shielding the 1s electron, therefore
22
the energy of the electron when it is in the 1s orbital is about 2.18 aJ( 2 ) 8.7 aJ, and
1
energy released on emission is > 8 aJ.
Then 1 represents a photon with energy less than 4 aJ; 0 represents a photon with more
than 8 aJ. 0 is therefore shorter than 1 by about a predicted factor of two.

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Some possibly useful facts:

For the one-electron atom with nuclear charge Z, the Bohr energy of the nth electronic state is
Z2
n2

En = 2.18 aJ

and the Rydberg formula for the wavelength of emitted/absorbed light in a one-electron atom is
1
1
1
= Z 2 (1.097 107 m1 ) ( 2 2 )

n1 n2
for n1 and n2 the two energy levels of the one-electron connected by the photon at wavelength ,
where n1 < n2 .
2
Zeff
(n, `)
For all atoms, E(n, `) = 2.18 aJ
n2
(p)(x)

h
;
4

h
mv

or

h
p

The mass of the neutron is mn = 1.675 1027 kg; the mass of the proton is mp = 1.673 1027 kg
The mass of the electron is me = 9.109 1031 kg;
NA = 6.022 1023
P V = nRT

where

R = 0.0821

`torr
`atm
= 63.36
molK
molK

Kelvin degrees = 273.15 + Celsius Degrees

Ephoton = h =

hc
;

1 watt = 1 Joule/sec = 1 kgm2 /sec3

h = 6.626 1034 Joulesec

c = 2.998 108 meter/sec

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