51

THE ATOMIC SPECTRUM OF HYDROGEN
When atoms are excited, either in an electric discharge or with heat, they tend to give off light. The light is emitted only at certain wavelengths that are characteristic of the atoms in the sample. These wavelengths constitute what is called the atomic spectrum of the excited element and reveal much of the detailed information we have regarding the electronic structure of atoms. Atomic spectra are interpreted in terms of quantum theory, which states that atoms can exist only at certain states that correspond to fixed energy levels. When an atom changes its state, it must absorb or emit an amount of energy that is just equal to the difference between the energies of the initial and final states. This energy may be absorbed or emitted in the form of light. The emission spectrum of an atom is obtained when excited atoms fall from a higher to a lower energy level. Since there are many such levels, the atomic spectra of most elements are very complex. Light is absorbed or emitted by atoms in the form of photons, each with a specific amount of energy, E. This energy is related to the frequency (ν) and wavelength (λ ) of light by the following equation: hc E photon = h! = " -34 where h = Planck's constant = 6.62608 x 10 J⋅s and c = speed of light = 2.997925 x 108 m / s The law of conservation of energy states that total energy is conserved. Thus, the change in energy of the atom must equal the energy change of the photon emitted. The energy change of the atom is equal to the energy of the upper energy level minus the energy of the lower level.

The amount of energy in a photon given off when an atom changes from one level to another is very small, of the order of 10-19 joules. To avoid working with such small numbers, we will work with one mole of atoms. The above equation is multiplied by Avogadro's number, N:

The above equation is useful in the interpretation of atomic spectra. For example, in the study of the atomic spectrum of sodium, a strong yellow line of wavelength 589.16 nm is observed. The above equation can be used to determine the change in energy. This in turn is corresponded to the transition in energy levels. The simplest of all atomic spectra is that of the hydrogen atom. In 1886 Balmer showed that the lines in the spectrum of the hydrogen atom had wavelengths that could be expressed by a rather simple equation. In 1913, Bohr explained the spectrum on a theoretical basis with his model of the hydrogen atom. According to Bohr's theory, the energies allowed to a hydrogen atom are given by the so-called Bohr's Equation:

where B = a constant (1312.04 kJ/mol) and n = the quantum number (1, 2, 3, ...)

It should be possible to draw a smooth curve through the plotted points. Given both the energy levels and the wavelengths. Determine the quantum numbers for the initial (nhi) and final (nlow) states for these transitions. no formal typed laboratory report is due this week. reassign the lines to scale readings and replot. Be careful handling the discharge tube. If your graph does not make a smooth curve. Create a calibration curve of wavelength versus the scale reading. Note that all the energies are negative.52 Bohr's equation allows you to calculate quite accurately the energy levels for hydrogen. observe the spectrum of a helium and a hydrogen discharge tube. Additionally. These wavelengths are also known very accurately. It will become quite hot during the course of the experiment. Transitions between these levels give rise to the wavelengths in the atomic spectrum of hydrogen. so that the lowest energy will have the largest allowed negative value. you have either made an experimental error or you have not identified the lines properly. calculate the energy levels (ε n) in kJ/mole for each of the eight lowest allowed levels of the hydrogen atom starting with n=1 to n=8. the discharge apparatus should not be touched when on. violet and light violet. Note that you must use the same apparatus for both discharge tubes. In the latter case. You can look up the values for the wavelength s of the four lines in the hydrogen spectrum in your textbook and calculate the percent error for each line. For Hydrogen. you will examine the spectrum of helium in which the wavelengths of the emission lines are known. intense blue. Be careful not to bump the apparatus! Helium: The scale reading the angle of refraction will have to be calibrated in terms of wavelength. your task will be to measure the wavelengths of the hydrogen spectrum and then determine the transition in energy levels associated with each wavelength. . To do this. record the scale reading and color of the four lines in the visible spectrum of hydrogen: intense red. PROCEDURE: Part A: Using the apparatus as demonstrated by your instructor. This lab consists of a worksheet that needs to be completed for credit. Locate the visible emission spectrum of helium and record the scale reading (an angle) for the seven lines in the helium spectrum. Using Bohr's equation. it is possible to determine the actual levels associated with each wavelength. Use the calibration curve you created for the helium spectrum and interpolate the wavelengths of the hydrogen lines. The energy levels will allow you to determine the energy transition (Δ E) that corresponds to the observed wavelengths. In this experiment. it operates under high voltage. Set up the discharge tube and prism as diagrammed below. Include the graph in your final lab report. Notice that there are distinct colored lines and that they are at different places on the calibration scale. In Part B you can use your experimentally determined wavelengths to calculate the energy change for each line in the observed hydrogen spectrum.

above. Make sure that the graph occupies at least 75% of a regular sized piece of paper.3_ _486. Color of Line red red yellow bright green blue-green blue violet bright violet Wavelength (nm) 706. to calculate the wavelengths of the four scale readings for hydrogen. Recall: Percent Error = absolute value (theoretical value .1_ _410. nm) ____________ ____________ ____________ ____________ λ (theoretical.experimental value) * 100% theoretical value ! . Determine the Percent Error for each of the four hydrogen transitions.53 The Atomic Spectrum of Hydrogen: Worksheet Complete the following worksheet using the instructions provided. Record all scale readings with five significant digits.8 587.2 471.6 492.1 Scale Reading (° ) ____________ ____________ ____________ ____________ ____________ ____________ ____________ Construct a calibration graph of wavelength versus scale reading constructed from the Helium spectrum data.6 501. nm) _656. Colorλ Red Blue Violet Violet Scale Reading (° )λ ____________ ____________ ____________ ____________ λ (graph.3 447.2_ Percent Errorλ ___________ ___________ ___________ ___________ Use the calibration graph from the helium spectrum. It should be possible to draw a smooth curve through the plotted points. A piece of graph paper is included at the end of this lab. Name: Lab Partner(s): Part A: Helium Spectrum – Determine the scale readings for the helium wavelengths in lab.1_ _434. Spectrum of Hydrogen – Determine the scale readings for the hydrogen wavelengths in lab.5 667.

04 kJ/mol Example: The n=2 energy level can be calculated as follows: εn = (-1312. .03 kJ/mol If your calculated value of ΔE is about –984.04 kJ/mol.04/12) = -1312. εn.1_ _434.010 _ _ _ _ n value 5 6 7 8 ε n (kJ/mol) _ _ _ _ _ _ _ _ Convert the wavelength values into ΔE (in kJ/mol) using the following equation: The calculated ΔE values correspond to a transition between the various energy levels.e. then your nhi would be 2 (the higher value of n) and your nlow value would be 1 (the lower value of n).2_ ν (s-1) ________ ________ ________ ________ Δ E (J/photon) ________ ________ ________ ________ Δ E (kJ/mol) _____________ _____________ _____________ _____________ nhiλ _____ _____ _____ _____ nlowλ _____ _____ _____ _____ ε n (kJ/mol) -1312.04 -328. The energy level.54 Part B: Calculations for the Energy Levels of Hydrogen Atom Find the energy level εn (in kJ/mol) for each quantum number from 1 through 8 using the following equation: "n = -1312. Determine which transition they correspond to by finding the change in energy (i.010 kJ/mol ! n value 1 2 3 4 Now complete the table below.010 kJ/mol. Δ E. Colorλ red blue violet violet λ (actual. Example: Find the change in energy in a transition of hydrogen between the n=2 and n=1 energy levels. corresponds to the final energy state minus the initial energy state. εn.εinitial = ε1 . and the energy level.1_ _410. ΔE) between levels. nm) _656.04/22) = -328. or: ΔE = εfinal .04 (kJ/mol) n2 Example: The n=1 energy level can be calculated as follows: εn = (-1312.03 kJ/mol. A change in energy. εn. calculated previously.04 – (-328. for n=2 is –328.ε2 = -1312.3_ _486. for n=1 is –1312.010) = -984.

since both species have only one electron. The helium ion. Calculate the energies in kJ/mole for the four lowest energy levels of the helium ion using the equation above. has energy levels similar to those of the hydrogen atom.04 to find ΔE in kJ/mol. The maximum electron energy that a hydrogen atom can have is 0 kJ/mole.90 nm Δ E (kJ/mol) nhi nlow .12 nm 468. What common characteristic do the lines in the Balmer series have? 2. he was limited experimentally to wavelengths in the visible and near ultraviolet regions from 250 nm to 700 nm. n=1. He+. ε1 ________ ε2 ________ ε3 ________ ε4 ________ 4. Find the quantum numbers of the initial and final energy states for the transitions that give rise to these three lines: λ 121. When Balmer found his famous series for hydrogen in 1886. as in your experiment. The energy levels of the helium ion are given by the following equation: 3. the electron is in its lowest energy state. (Hint: ΔE = ε1 . How much energy does it take to ionize one hydrogen atom in kilojoules per mole and in Joules per atom? (Hint: calculate ΔE where εfinal is zero and εinitial is –1312. at which point the electron would essentially be removed from the atom and it would become a H+ ion. Three of the strongest lines in the helium ion spectrum are observed at the following wavelengths.ε2). Use the equation in Part B of the worksheet to calculate the wavelength (in nm) of this transition. 5. One of the most important transitions for the helium ion involves a jump from the n = 2 to the n = 1 level. Calculate the change in energy in kJ/mole for this transition.) Questions #3 through #5 will use the equation below for the helium ion.57 nm 164.55 Post Lab Questions: 1. In the hydrogen atom.

56 .

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