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# CHEMISTRY 2090

PRELIM I

October 8, 2015

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2:3 or anything similar. Other than the substitution of Z where it used to say P. One such compound is analyzed and found to contain 77. this was a clicker question. 85. 3:2. if you did not receive full credit you might wish to submit your exam for reconsideration. (8 points) An unknown atom Z forms multiple chlorides with the generic formula Zx Cly .1% Cl by mass. a second. 6:10. For those of you with answers for the ratio of 10:6.1. the answer given in class is shown below.5% Cl by mass. 2 . Show that these compounds conform to Dalton’s law of multiple proportions.

45 × 1021 = 1. (a) (5 points) If 7. what is the element X? One mole of atoms contains 6.45 × 1021 atoms represents 7. What was the minimum number of photons/second which were required for a signal to register at the antenna? Energy/photon is hν = (6.2.526 × 10−24 J/photon 3 .10 g.238 × 10−2 moles of atoms. One mole therefore has mass 6. Suggesting the atom is Y. with mass 1.10 g = 88.11 × 10−21 J/s So the antenna requires an input of = 744 photons/s.26 × 10−25 = 5.02 × 1023 1.9 g/mole.238 × 10−2 mole (b) (5 points) Radio signals sent from the first NASA flight to Jupiter. were transmitted at a frequency of 8. 5.10 g.02 × 1023 atoms.45 × 1021 atoms of an unknown element X has mass 1.11 × 10−21 watts (1 W = 1 J/s = 1 kg-m2 /s3 ).34 × 109 /s) = 55.526 × 10−24 J/photon. so our sample of 7. in the late 1970’s.626 × 10−34 J−s)(8. 1.34 × 109 s−1 . 4. The receiving antenna on earth was capable of detecting 4.

We also know that the DeBroglie wavelength is given by h h h = . After taking the square root. What is observed? hc Nothing. Call it 2. is equal to the distance it travels in one second. not more low energy photons iii.3. λ. red photons carry less energy/photon than is found in green photons. we find v = . Output of photoelectrons requires higher energy photons.753 × 10−18 J 264 nm is found in the ultraviolet–where green light is at longer wavelengths (500-600 nm). we λ= p me v me v h 6.626 × 10−34 J−s)(2. What will be observed? Still nothing. at lower energy. ii. (a) (4 points) An electron is found to have a velocity such that its wavelength.753 aJ. (b) (6 points) An intense beam of green light shines on a copper metal surface whose threshold energy for the photoelectron effect is 0.274 × 10−4 m2 /s2 . Output of photoelectrons requires higher energy photons. 4 . The intensity of the beam is doubled. Rearranging. The threshold energy of 0.7 cm. we can combine what we know to give v × 1 s = . What will be observed? Still nothing. What is its velocity? We are told that λ = v × 1 s.02697 m. i.38 × 10−8 m = 264 nm E 0.998 × 108 m/s) hc = = 26.626 × 10−34 J−s find v 2 × 1 s = = . cancelling common units (remember that the J me 9. The green light of part (i) is replaced with an equally intense beam (same number of photons/second) of red light.753 aJ/photon (E = ) corresponds to a photon λ wavelength of λ= (6.109 × 10−31 kg is a kg-m2 /s2 !) leads to v 2 = 7.

1 1 1 atm of O2 . and we use up all the NH3 5 (1.00 ` and we assume 100% yield in the reaction as written? The ideal gas law PV = nRT tells us that at fixed T. and 3 2 12 5 . atm of water. or 1. the product PV is proportional to the number of moles.4.00 `-atm of NH3 . all measurements of pressure are made at T = 137◦ C.50 atm. 4 moles of NH3 react with 5 moles of O2 . The valve is opened and the reaction proceeds as the gases mix. Flask A contains 2. Flask B contains 1. Flask A contains 1. 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. Producing 1. What is the partial pressure of NO produced.500 atm.25 `-atm of O2 .50 `-atm of H2 O. if the final container volume is 3.00 `-atm) and as much of the O2 .00 `-atm of NO 4 and 1. so we have atmosphere of NO.00 ` of NH3 at 0. (a) (8 points) Nitric acid is produced commercially by the Ostwald process.50 `-atm of O2 . We could calculate n directly but it is less work to just find PV. so the NH3 is limiting. Final volume is 3 liters. B contains 1.00 ` of O2 at 1.

6 . x.41 mg of H2 O. it is a deadly poison. y and z for Cx Hy Nz ) if upon combustion of 4.9 mg of CO2 and 3. Find the empirical formula of nicotine (that is.40 mg of nicotine one collects 11. In large quantities.(b) (8 points) Even in small quantities nicotine as found in tobacco is addictive.

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. (10 points) 10.5. What is the mass of each compound in the orginal mixture? 7 .91 atm.0 grams of a mixture of Ca(ClO)2 and Ca(ClO3 )2 are placed in 10.

(or if you plugged in the value of something that looks like c∆x ≥ 4π c = ∆v) you should have received 3 points in partial credit. (b) (5 points) An atom is observed to emit light at 100. 8 . and 500.6. What is the minimum uncertainty. (a) (5 points) No object can travel faster than the speed of light. More was provided for the energy level diagram showing the relationship between the states. and simply wrote h . how far above the ground state are the excited states? A small amount of partial credit was given for calculating the energies of transition. With our apologies. nm. nm. ∆x. If you didn’t please submit for a regrade. c. if we know only that its velocity is less than c? For those of you who left out me from the expression. In aJ. and why there were three transitions with only two excited states. 125. ∆v can never be greater than 3 × 108 m/s. Theory predicts that only the ground state and two excited states are involved. nm. so the uncertainty in the velocity. in the position of an electron.

therefore y = 6 so as to keep balance of the hydrogen atoms. The density measures the mass of the units as they exist in the gas phase.0. (a) (7 points) The element arsenic (As) forms an oxide with formula Asx Oy which can be studied as a gas. (The same result holds even if you don’t assume identical volumes.e. Container Y has half the density in g/liter of container X. as the density is measured per liter. Is this an empirical or molecular formula? (Explain your answer). one contains gas X. The two gases behave as ideal gases and are at the same temperature. so the molecule density in any specified volume in Y is also one-quarter the density in the same volume in X.6–which is within the uncertainty bounds 397 ± 3. in g/`.) 9 . and that (ii) six volumes of gaseous hydrogen H2 react with one volume of gaseous Asx Oy to form elemental arsenic and water. We also have the result Asx Oy + 6 H2 → x As + y H2 O. The atomic mass of As is 74.0) then its molecular weight must be (12. 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.1) × 32. identify as best you can x and y): If the density of our unknown gas is 12.7. ii. The formula of the gaseous Asx Oy (i. Under the same conditions of temperature (T ) and pressure (P ) it is found that (i) the density of the gaseous Asx Oy is 12. is half that of X.4 ± 0. there must be one-quarter as many molecules of gas Y in container Y as there are or molecules of X in container X. The ratio of volumes is the same as the ratio of moles of reactants. i. Gas Y has double the molecular mass of gas X. The molecular mass of Y is double that of X. the pressure in Y is one-quarter that in X. T .0 = 397 ± 3 g/mole.9. As each unit of gas Y has double the mass. Find the ratio of the pressure of X to the pressure of Y . that of O. the second.4 times that of O2 (with molecular weight 32. As the pressure is proportional to the number of molecules (for fixed temperature and identical volume). The density of gas Y . 16.4 times the density of gaseous O2 . gas Y . The only combination of x and y = 6 that comes close is As4 O6 with mass 395. This is molecular.

` = 2 There are no possible orbitals. ms = − Following the logic above. or ` = 1. and four possible electrons with the specified quantum numbers. There are three possible ` values for n = 3. n = 3. ms } or {3. `. we seek allowed orbitals with quantum 2 1 numbers {n = 2. For m = 1 we are limited to only ` = 1 or ` = 2. 2 with m = −1. m = 1 We are asked how many electrons can have the four quantum numbers {n = 3. and black to high probabilites Which values of n and ` do these orbitals represent? (Put your answers on the lines below the illustrations. or 2. n = 2.) 4d 4p (c) (2 points) Consider the orbitals listed below. ` can take on values ` = 0. n = 2. with spin ms = ± Four electrons 2 can have these quantum numbers. that is. ` = 2. m. m = 1. 1. 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 10 . Each of the two orbitals 1 {3. with m = 0. iv. 1 ii. (a) (4 points) How many electrons can have the sets of quantum numbers indicated below? i. ` = 2 requires n ≥ 3. m = 2 These quantum numbers describe one specific orbital. ms }. ` = 0. the number of radial nodes and the number of angular nodes found. in each in the appropriate columns. Enter the total number of nodes. There are four possible orbitals. 1. iii. with ms = ± . 1. 1.8. n = 4. 2 (b) (4 points) Below are shown pictures of Ψ2 for two H-atom orbitals. `. ms } can house two electrons. 2. 0 or m = 1. ms = − }. white areas correspond to low probabilities. it can 1 house two electrons.

Electrons are drawn as arrows.(d) (3 points) Below are drawn a number of possible electronic configurations for the 8 electrons found in an oxygen atom (O). 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. whose direction indicates the value of the spin quantum number ms . (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 λ which can be observed in this series of lines? 11 . or “forbidden” if the configuration cannot exist. “ground” if it represents the ground state. 9.

18 aJ( 2 ) ≈ −8. λ0 is therefore shorter than λ1 –by about a predicted factor of two. the worst case. For which pair of energy levels ni and nf does the 434. in the excited and ground state. In the doubly-excited state. the energy of the electron in the 5s orbital should 12 be approximately −2. In the 1s orbital. describe how Zeff varies for the various electrons in the different states. Would you expect λ0 to be larger. but. we also need to double n. In the ground state.0 nm is found in He+ for ni = 10 and nf = 4.0 nm corresponding to the emission of light as an excited H atom relaxes between the ni = 5 and nf = 2.18 aJ( 2 ) ≈ −0. In the excited state. λ0 represents a photon with more than 8 aJ. if we double Z in going from H to He+ . instead. the 5 ionization energy of the He atom is about 3. The same line is observed in the He+ spectrum. or. n2 So to get transitions at the same energy. where there is no shielding. and therefore the transition energy should be the difference between the energies of the two states: about 4 aJ (I’m being loose as all we really need are rough estimates!). and 1 energy released on emission is > 8 aJ. it should be approximately hydrogen-like with Zeff > 1 because the two 5s electrons partially shield one another.9 aJ. 12 . or the same as λ1 observed for the transition from the singly excited state 1s1 5s1 → 1s2 ? (You should not try to be quantitative.) For the transition 1s1 5s1 → 1s2 we need to consider the energies of the electron undergoing the transition.0 nm line appear in He+ ? Z2 in the one-electron atom with nuclear charge Z. So the same line at 434. therefore 22 the energy of the electron when it is in the 1s orbital is about −2.7 aJ. The doubly-excited He atom emits a photon at λ0 when it undergoes the transition 5s2 → 1s1 5s1 . For the transition 5s2 → 1s1 5s1 one electron is making the same transition. and then the energy of either electron in the 5s orbital should be approximately 22 −2. for purposed of argument I’ll choose Zeff = 2.35 because each of the 1s electrons partially shields the other. Then λ1 represents a photon with energy less than 4 aJ. the electron sees effectively the full nuclear 5 charge Zeff ≈ 2 because the 5s electron is ineffective at shielding the 1s electron.35 aJ. Zeff ≈ 1. smaller. 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.18 aJ( 2 ) ≈ −0. if you prefer.(b) (3 points) In the spectrum of the H atom. as we said in class. that is. there is a blue line observed at 434. but in a very different background.09 aJ. 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 . it won’t really matter. we need to simply keep the ratio Z/n fixed.

2 Zeff (n. the mass of the proton is mp = 1.109 × 10−31 kg.15 + Celsius Degrees Ephoton = hν = hc . λ 1 watt = 1 Joule/sec = 1 kg−m2 /sec3 h = 6.673 × 10−27 kg The mass of the electron is me = 9. NA = 6.022 × 1023 P V = nRT where R = 0.626 × 10−34 Joule−sec c = 2.36 mol−K mol−K Kelvin degrees = 273. `) For all atoms. `) = −2.Some possibly useful facts: For the one-electron atom with nuclear charge Z. where n1 < n2 .097 × 107 m−1 ) ( 2 − 2 ) λ n1 n2 for n1 and n2 the two energy levels of the one-electron connected by the photon at wavelength λ.18 aJ n2 (∆p)(∆x) ≥ h .0821 `−torr `−atm = 63. 4π λ= h mv or λ= h p The mass of the neutron is mn = 1. the Bohr energy of the nth electronic state is Z2 n2 En = −2.998 × 108 meter/sec 13 . E(n.18 aJ and the Rydberg formula for the wavelength of emitted/absorbed light in a one-electron atom is 1 1 1 = Z 2 (1.675 × 10−27 kg.