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5.111 Extra Problems for Exam I

Here are some extra problems that you can work as preparation for the first exam on Friday October 7th, 2011. Be sure that you have already studied the material before you attempt these problems. Approach each problem as an exam problem. Many of these problems are former exam problems. Remember that rephrasing the problem in your own words or drawing a sketch of the problem often helps crystallize the physical concept behind the problem. Once you understand the physical principle behind the problem, the equations necessary to work the problem will come to you easily. Remember, there are a limited number of physical principles being tested here. Dont rely on a fixed, memorized procedure or memorized equation to solve a problem. You cant always make a problem fit into the procedure or equation that you have memorized. You have to modify the procedure or the equation to fit the problem. Dont modify the problem to fit the equations! Dont deny yourself the opportunity to intellectually engage and mentally wrestle with these problems by looking at the solutions first. You wont have this opportunity on the exam. Remember, you cant learn to work a crossword problem by looking at the solutions! Also remember that looking at a map is a very different experience than actually driving the roads! 1. Photons of wavelength 315 nm or less are needed to eject electrons from a surface of electrically neutral cadmium. (a) What is the energy barrier that electrons must overcome to leave an uncharged piece of cadmium? (b) What is the maximum kinetic energy of electrons ejected from a piece of cadmium by photons of wavelength 2.00 102 nm? (c) Suppose the electrons described in (b) were used in a diffraction experiment. What would be their wavelength? 2. Calculate the energy (in J) of a photon whose period is 5 x 10-15 s. 3. Calculate the probability of an electron in the 2p state of an H atom being at a distance between r = 4.0000ao and r = 4.0000ao + 0.0001ao. 4. The sodium D-line is actually a pair of closely spaced spectroscopic lines seen in the emission spectrum of sodium atoms. The wavelengths are centered at 589.3 nm. The intensity of this emission makes it the major source of light (and causes the yellow color) in the sodium arc light. If a sodium arc light is to produce 1.000 kilowatt (1000. J/s) of radiant energy at this wavelength, how many moles of sodium atoms must emit photons per second? 5. Potassium has a work function equal to 3.69 10-19 J. How many photoelectrons will be produced under each of the following illuminations? (a) Light with a wavelength of 538 nm delivers a total energy of 3.69 10-16 J. (b) Light with a wavelength of 500. nm delivers a total energy of 3.97 10-16 J. (c) Light with a wavelength of 600. nm delivers a total energy of 3.31 10-14 J. 6. Excited by electromagnetic radiation with a wavelength of 827 , an electron is stripped from a ground state H atom. (a) How much kinetic energy does the liberated electron possess after ionization? (b) Calculate its velocity. (c) Calculate its wavelength.

Extra Problems for Exam 1 for 5.111 Page 2 of 9 7. An electron is hit by an x-ray photon and it consequently moves faster. Does the wavelength of the light increase, decrease or remain the same? What happens to the wavelength of the photon? 8. The energy needed to ionize an atom of element X when it is in its most stable state is 5.00 102 kJ/mol. However, if atom X is in its lowest excited state, only 1.20 102 kJ/mol is needed to ionize it. What is the wavelength of the radiation emitted when an atom of X undergoes a transition from the lowest excited state to the ground state? 9. Calculate the shortest and the longest wavelength of light emitted when the H atom makes a transition from the n=6 state. 10. A free electron moves with a velocity v = 1.00x106 m/s before being captured by a hydrogen nucleus. Eventually, it lands in the 1s orbital. What is the change in its energy? 11. Consider Ne+9. What is the wavelength of the photon emitted when the electron goes from the 6p orbital to the 2s orbital? 12. Calculate the ratio of the probabilities of finding the 1s electron of a H atom in a spherical shell of thickness dr at r=ao to that at r=1x10-4ao. 13. The ionization energy of a certain one-electron atom is 3.28 x 104 kJ/mol. How many protons are contained in the nucleus? + 2+ 8+ 14. Consider the following ions: He , Li , F . 9+ (a) Calculate the energy released in kJ/mole when an electron initially far from a F ion combines 8+ with it to make an F ion with the electron in the lowest orbital. 2+ (b) Calculate the frequency in Hz for the n=6 to n=2 transition in Li . + (c) How any different states (i.e. sets of quantum numbers) are possible for He with n=6? Specify the l and m values. + 15. The ionization energies of He, H, and He are 3.989 10-18 J, 2.179 10-18, and 8.719 10-18 J, respectively. Give reasons for the relative values of these ionization energies in terms of the expression for the binding energies of one electron atoms and electron-electron repulsion. 16. Give the number of radial and angular nodes for the following hydrogen orbitals: (a) 7f (b) 7s (c) 7p 17. At r=0, the PROBABILITY DENSITY of a H atom wavefunction has a non-zero value. In addition, the probability density associated with this wavefunction is zero for at least one non-zero value of r. Of the possible wavefunctions from n = 1 through n = 4 and from = 0 through = 1, name all of the wavefunctions that are consistent with these probability densities. The name of the wavefunction should consist of the principal quantum number, a letter such as s, p, d, f, and, if appropriate, a letter such as x, y or z. 18. An atom of sodium has the electron configuration [Ne]6s1. Explain how this is possible. 19. Which should experience the greater effective nuclear charge, a 2p electron in oxygen or a 2p electron in neon? 20. Without attempting a detailed calculation, estimate the highest value and the lowest value for the first ionization energy for a ground state He atom. 2

Extra Problems for Exam 1 for 5.111 Page 3 of 9 21. The most probable value of r for the 3p state is smaller than that for the 3s state. Why is the energy of the 3s state lower than that of the 3p state in a multielectron atom? 22. The photoelectron spectrum of Mg is measured using X-ray photons of energy 600.0 x 10-18 J. Electrons are emitted from the Mg atoms with the following kinetic energies (in units of 10-18 J): 598.8, 591.4, 585.3, 391.0. (a) Write the ionization processes responsible for each of these kinetic energies. (b) Calculate the binding energies for the filled orbital of Mg (c) Al+ is isoelectronic with Mg. Do you expect the binding energies in Al+ to be weaker or stronger than in Mg? Explain. 23. The five successive ionization energies of B (i.e IE1 through IE5) are 800, 2420, 3660, 25020 and 32820 kJ/mole. a) Write equations for these ionization processes giving the electron configuration before and after the ionization. b) Write equations for these ionization processes seen in the photoelectron spectrum of B, giving the electronic configuration before and after the ionization. 24. In the second period of the periodic table, there are atoms with a negative electron affinity. Identify two of these atoms and explain why the electron affinity is negative. 25. Arrange the following in order of size from the smallest to the largest: I , Br , Cl , Cl, Mg2+, Ne. 26. Consider the following ions: He , Li , F . a) Which has the smallest radius? Explain. b) Which has the highest IE1? Explain. c) Which has the largest EA? Explain.
+ 25+ + 2+ 8+

27. Arrange the following seven atoms or ions in order of size: K, F , Rb, Co , Br, F, Rb . 28. Predict the larger ion in each of the following pairs. Give reasons for your answers. a) O, S2 b) Mn2+, Mn4+ c) CO2+, Ti2+ d) Ca2+, Sr2+ 29. Consider the atoms As, Cl, K and S. a) Which atom has the greatest electron affinity? b) Which atom has the lowest electron affinity? 30. The first ionization energy of helium is 2370 kJ mol1, the highest for any element. a) Define ionization energy and discuss why that for He should be so high. b) Which element would you expect to have the highest second ionization energy? Why? c) Suppose that you wished to ionize some helium by shining electromagnetic radiation on it. What is the maximum wavelength you could use? 31. Without consulting any tables, arrange the following substances in order and explain your choice of order: a) Mg2+, Ar, Br, Ca2+ in order of increasing radius. b) Na, Na+, O, Ne in order of increasing ionization energy. c) H, F, Al, O in order of increasing electronegativity. 32. a) Order the elements S, Cl, Ar, K, Ca, Sc, Ti from lowest to highest ionization energy. b) Order the elements S, Cl, Ar, K, Ca, Sc, Ti from lowest to highest second ionization energy.

Extra Problems for Exam 1 for 5.111 Page 4 of 9 33. Two loudspeakers (shown below as ) broadcasting in phase at the same frequency are 1.829 m from each other. You are positioned 3.048 m directly in front of one of the speakers. Calculate the lowest frequency sound wave that will result in a maximum intensity of the sound that you hear. Recall that the speed of sound is 343 m/s. (No equations given.)

34. Consider two photoelectric effect experiments on Cs metal. One experiment uses a 1.00 102 W green lamp with a wavelength of 530.6 nm and the other uses a 5.00 102 W blue lamp with a wavelength of 460.5 nm. (1W = 1 J/s) a) Calculate the work function of Cs if the 1.00 102 W green lamp with a wavelength of 530.6 nm produces electrons with an energy of 7.01 10-20 J. b) Calculate the wavelength of the electrons emitted in part (a). c) Calculate how many photons per s are being emitted by the 5.00 102 W blue lamp with a wavelength of 460.5 nm. d) If the Cs metal is exposed to the 1.00 102 W green lamp with a wavelength of 530.6 nm for 1.0 min, calculate how long must the Cs metal be exposed to the 5.00 102 W blue lamp with a wavelength of 460.5 nm to eject the same number of electrons. 35. Suppose that you carry out a Rutherford backscattering experiment on one monolayer of quantum dots of uniform diameter. Through the wonders of nanotechnology, these quantum dots are held so that they do not abut against each other, and the distance between the dots is random. The particles are impervious to the quantum dots. That is, they do not pass through the quantum dots, but they do pass through the space between the dots. The particles impinge on a total surface area of 5.0 10-3 m2. There are 1.20 1013 randomly spaced quantum dots in this total surface area. If the probability of backscattering of the particles is 0.3147, calculate the diameter of the quantum dots. Show your work for full credit. (No equations given.) 36. Suppose an atom has electrons with 9 different values of Zeff, as listed below. (You can use the periodic table without electron configurations). 37.19 22.17 34.03 13.44 27.90 11.93 22.73 6.07 22.66

a) Identify the atom. b) The value of m for one of the electrons with Zeff = 22.17 is 2. What is its probability density at r=0? 4

Extra Problems for Exam 1 for 5.111 Page 5 of 9 c) How many angular nodes does the wavefunction for the electrons with Zeff = 22.17 have? d) Draw the radial probability distribution for the electron with Zeff = 11.92. The relative magnitudes of the extrema and nodes must be correct, if there are multiple extrema and nodes. Label your axes. Indicate the origin on both the y and x axes. 37. Short answer. You can use a periodic table (without electron configurations) for part (a). a) Write the ground state electron configuration of Ta+. You can use the inert gas configuration as a means to abbreviate the configuration. You do not have to list the electrons in the individual m states of the p, d or f orbitals. b) Consider the ni = 2 to nf = 3 transition in C+5 and in O+7. Does this transition in O+7 require a photon with the same momentum, a smaller momentum or a larger momentum as the transition in C+5? (You may Z2 R H 1 1 ). refer to = 2 2 h n i nf c) The numerical values of a wavefunction for a one-electron atom at three values of r are (r = ao) = 0.92, (r = 2ao) = -0.25 and (r = 6ao) = 0.13. Of the 1s, 2s, 3s, 4s and 5s wavefunctions, which of these wavefunctions are not consistent with this description? (No equations given.)

Extra Problems for Exam 1 for 5.111 Page 6 of 9 After you have studied for the exam and worked on the above extra problems, you should try to complete the following 5 problems in 50 minutes, without aid of notes or the text. You may use a periodic table without electron configurations. A. 1-electron atoms and wavefunctions Question 1: Radial probability distribution (RPD) functions.
a.

Based on its qualitative features, what H atom wavefunctions with n up to 6 could have the RPD function sketched below? If there are multiple wavefunctions, indicate them all. You dont need to indicate all the orbitals with different m values, e.g. if it were correct you would write 6p but not 6px, 6py, 6pz.

RP D r

b.

RPD1, RPD2, and RPD3 are the same qualitatively as the RPD above, but they are compressed to smaller values or expanded to larger values of r.

RPD1 r
H atom Li2+ ion

RPD2 r

RPD3 r

Assume the RPDs describe an electron in the same orbital (i.e. with the same quantum numbers) for the following three species.

Na (neutral) atom in its normal (lowest-energy) electron configuration Match the RPD with the atomic species. Indicate your answers by writing RPD1, RPD2, or RPD3 next to each of the above atomic species. Question 2: What is the maximum number of electrons in an atom that can have the following quantum numbers?
a. b. c. d.

n=4 n = 5, m = 1 n = 3, = 2 n = 1, ms = 1/2

Extra Problems for Exam 1 for 5.111 Page 7 of 9 Question 3:The relationship between spherical polar coordinates (r, , ) and Cartesian (x,y,z) is shown here:

Using this information, answer (i), (ii), and (iii) for each H atom wavefunction (a), (b), and (c) below. Write your answers next to or just below the wavefunctions (a), (b), & (c). (i) Give the number of radial and angular nodes in each wavefunction. (ii) For what values of r, , and are these nodes present? (iii) Label each wavefunction (for example, 2s, 3pz, etc). 3/ 2 1/ 2 1 1 r r 2a o 1 a. = 2 a e 4 2 2 ao o
b.

1 1 = 2 6 ao = 1 1 2 6 ao

3/ 2

r r 2a o 3 e ao 4 r r 2a o 3 e ao 4

1/ 2

cos sin sin

3/ 2

1/ 2

c.

B. Light, waves, and spectroscopy Question 4: Calculate the final state (n quantum number) of a hydrogen atom that starts in the ground state, absorbs a photon of wavelength 97.2 nm, and then subsequently emits a photon of wavelength 486.1 nm. You must show your work on this problem to get any credit. (Note: This calculation involves several steps. You might consider saving the calculation until you finish the rest of the exam. You can get partial credit by indicating the steps and the expressions you will use. ) Question 5: (a) X-ray photons of energy 0.800 keV are incident on a sample of H atoms. Some of the atoms have their electron in the 1s orbital, some in the 2s orbital, and some in the 2p orbital. Electrons emerge from the different atoms in the sample with kinetic energies that are measured. (i) How many different values of the kinetic energy are measured? (ii) What are the values, in units of keV? (b) Visible photons of energy 10.0 eV are incident on copper metal whose work function is 4.7 eV. Electrons emerge with kinetic energies that are measured. (i) How many different values of the kinetic energy are measured? (ii) What are the values? (c) A beam of x-ray photons with wavelength 0.10 nm is directed at a very thin silicon crystal. A beam of electrons with the same 0.10 nm wavelength is directed at the same silicon crystal. In each case, part of 7

Extra Problems for Exam 1 for 5.111 Page 8 of 9 the incident beam is transmitted straight through the thin crystal without any deflection, and part of the incident beam is diffracted to a first-order diffraction spot. The angle between the undeflected beam and the diffracted beam is (circle one): greater for the x-rays greater for the electrons the same for both

C. Many-electron atoms and periodic trends Question 6: (a) Arrange the following in terms of increasing atomic radius: i. O, O-, O2ii. Mg2+, Ar, Br-, Ca2+ (b) X-ray photons of energy 0.800 keV are incident on a sample of carbon atoms in their normal (lowest energy) electron configuration, and electrons emerge with kinetic energies that are measured. How many different values of the kinetic energy are found? (c) Write the electron configurations for the following atoms. You may follow the convention of indicating the noble gas shell preceding the valence electrons. In addition to the electron configuration, indicate the number of unpaired electron spins, that is, the net number of spins in one direction that are not offset by spins in the opposite direction. electron configuration # unpaired spins a. Be b. Ti2+ c. Ge d. Ag (d) Circle the one atom out of the ten below that has the lowest second ionization energy. The atoms are displayed to show their relative positions in the periodic table. Na Mg S Cl Ar Rb Sr Te I Xe

Extra Problems for Exam 1 for 5.111 Equation sheet and periodic table for 5.111:

Page 9 of 9 c = 2.9979 x 108 m/s h = 6.6261 x 10-34 J s NA = 6.022 x 1023 me = 9.1094 x 10-31 kg ao = 5.292 x 10-11 m 1 amu = 1.66 x 10-27 kg
p2 E= 2m h = p RH = 2.1799 x 10-18 J Z2R H En = 2 n Z 2R E nl = eff 2 H n

1W = 1 J s-1 for s wavefunction: RPD = 4r22dr d2-d1 = n n = a sin for emission Z2R H 1 1 v= - 2 h ni n2 f for absorption.. Z2R H 1 1 v= - 2 h nf n2 i