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Page 1: CHAPTER 05- Atomic Structure.ppt

1

CHAPTER 5

The Structure of Atoms

Page 2: CHAPTER 05- Atomic Structure.ppt

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Chapter Outline

Subatomic Particles

1. Fundamental Particles

2. The Discovery of Electrons

3. Canal Rays and Protons

4. Rutherford and the Nuclear Atom

5. Atomic Number

6. Neutrons

7. Mass Number and Isotopes

8. Mass spectrometry and Isotopic Abundance

Page 3: CHAPTER 05- Atomic Structure.ppt

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Chapter Goals

9. The Atomic Weight Scale and Atomic Weights

The Electronic Structures of Atoms

10. Electromagnetic radiation

11. The Photoelectric Effect

12. Atomic Spectra and the Bohr Atom

13. The Wave Nature of the Electron

14. The Quantum Mechanical Picture of the Atom

Page 4: CHAPTER 05- Atomic Structure.ppt

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Chapter Goals

15. Quantum Numbers

16. Atomic Orbitals

17. Electron Configurations

18. Paramagnetism and Diamagnetism

19. The Periodic Table and Electron Configurations

Page 5: CHAPTER 05- Atomic Structure.ppt

5

Fundamental Particles

Particle Mass (amu) Charge

Electron (e-) 0.00054858 -1

Proton (p,p+) 1.0073 +1

Neutron(n,n0) 1.0087 0

Three fundamental particles make up atoms. The following table lists these particles together with their masses and their charges.

Page 6: CHAPTER 05- Atomic Structure.ppt

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The Discovery of Electrons

Humphrey Davy in the early 1800’s passed electricity through compounds and noted:– that the compounds decomposed into elements.– Concluded that compounds are held together by

electrical forces. Michael Faraday in 1832-1833 realized that the

amount of reaction that occurs during electrolysis is proportional to the electrical current passed through the compounds.

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The Discovery of Electrons

Cathode Ray Tubes experiments performed in the late 1800’s & early 1900’s.

– Consist of two electrodes sealed in a glass tube containing a gas at very low pressure.

– When a voltage is applied to the cathodes a glow discharge is emitted.

Page 8: CHAPTER 05- Atomic Structure.ppt

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The Discovery of Electrons

These “rays” are emitted from cathode (- end) and travel to anode (+ end).– Cathode Rays must be negatively charged!

J.J. Thomson modified the cathode ray tube experiments in 1897 by adding two adjustable voltage electrodes.– Studied the amount that the cathode ray beam was

deflected by additional electric field.

Page 9: CHAPTER 05- Atomic Structure.ppt

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The Discovery of Electrons

Modifications to the basic cathode ray tube experiment.

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The Discovery of Electrons

Thomson used his modification to measure the charge to mass ratio of electrons.Charge to mass ratio

e/m = -1.75881 x 108 coulomb/g of e-

Thomson named the cathode rays electrons. Thomson is considered to be the “discoverer of

electrons”. TV sets and computer screens are cathode ray

tubes.

Page 11: CHAPTER 05- Atomic Structure.ppt

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The Discovery of Electrons

Robert A. Millikan won the 1st American Nobel Prize in 1923 for his famous oil-drop experiment.

In 1909 Millikan determined the charge and mass of the electron.

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The Discovery of Electrons

Millikan determined that the charge on a single electron = -1.60218 x 10-19 coulomb.

Using Thomson’s charge to mass ratio we get that the mass of one electron is 9.11 x 10-28 g.– e/m = -1.75881 x 108 coulomb– e = -1.60218 x 10-19 coulomb– Thus m = 9.10940 x 10-28 g

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Canal Rays and Protons

Eugene Goldstein noted streams of positively charged particles in cathode rays in 1886.

– Particles move in opposite direction of cathode rays. – Called “Canal Rays” because they passed through holes (channels or

canals) drilled through the negative electrode. Canal rays must be positive.

– Goldstein postulated the existence of a positive fundamental particle called the “proton”.

Page 14: CHAPTER 05- Atomic Structure.ppt

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Rutherford and the Nuclear Atom

Ernest Rutherford directed Hans Geiger and Ernst Marsden’s experiment in 1910. - particle scattering from thin Au foils – Gave us the basic picture of the atom’s structure.

Page 15: CHAPTER 05- Atomic Structure.ppt

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Rutherford and the Nuclear Atom

In 1912 Rutherford decoded the -particle scattering information.– Explanation involved a nuclear atom with electrons

surrounding the nucleus .

Page 16: CHAPTER 05- Atomic Structure.ppt

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Rutherford and the Nuclear Atom

Rutherford’s major conclusions from the -particle scattering experiment

1. The atom is mostly empty space.

2. It contains a very small, dense center called the nucleus.

3. Nearly all of the atom’s mass is in the nucleus.

4. The nuclear diameter is 1/10,000 to 1/100,000 times less than atom’s radius.

Page 17: CHAPTER 05- Atomic Structure.ppt

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Rutherford and the Nuclear Atom

Because the atom’s mass is contained in such a small volume:– The nuclear density is 1015g/mL.– This is equivalent to 3.72 x 109 tons/in3.– Density inside the nucleus is almost the same as a

neutron star’s density.

Page 18: CHAPTER 05- Atomic Structure.ppt

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Atomic Number

The atomic number is equal to the number of protons in the nucleus.

– Sometimes given the symbol Z.– On the periodic chart Z is the uppermost number in each

element’s box. In 1913 H.G.J. Moseley realized that the atomic

number determines the element .– The elements differ from each other by the number of protons

in the nucleus. – The number of electrons in a neutral atom is also equal to the

atomic number.

Page 19: CHAPTER 05- Atomic Structure.ppt

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Neutrons

James Chadwick in 1932 analyzed the results of -particle scattering on thin Be films.

Chadwick recognized existence of massive neutral particles which he called neutrons.– Chadwick discovered the neutron.

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Mass Number and Isotopes

Mass number is given the symbol A. A is the sum of the number of protons and neutrons.

– Z = proton number N = neutron number– A = Z + N

A common symbolism used to show mass and proton numbers is

AuCa, C, example for E 19779

4820

126

AZ

Can be shortened to this symbolism.

etc. Ag,Cu, N, 1076314

Page 21: CHAPTER 05- Atomic Structure.ppt

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Mass Number and Isotopes

Isotopes are atoms of the same element but with different neutron numbers.

– Isotopes have different masses and A values but are the same element.

One example of an isotopic series is the hydrogen isotopes.

1H or protium is the most common hydrogen isotope. one proton and no neutrons

2H or deuterium is the second most abundant hydrogen isotope. one proton and one neutron

3H or tritium is a radioactive hydrogen isotope. one proton and two neutrons

Page 22: CHAPTER 05- Atomic Structure.ppt

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Mass Number and Isotopes

The stable oxygen isotopes provide another example. 16O is the most abundant stable O isotope.

• How many protons and neutrons are in 16O?neutrons 8 and protons 8

17O is the least abundant stable O isotope. How many protons and neutrons are in 17O?

18O is the second most abundant stable O isotope.How many protons and neutrons in 18O?

neutrons 9 and protons 8

neutrons 10 and protons 8

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Mass Spectrometry andIsotopic Abundances

Francis Aston devised the first mass spectrometer.– Device generates ions that pass down an evacuated path inside

a magnet.– Ions are separated based on their mass.

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Mass Spectrometry andIsotopic Abundances

There are four factors which determine a particle’s path in the mass spectrometer.1 accelerating voltage2 magnetic field strength3 masses of particles4 charge on particles

Page 25: CHAPTER 05- Atomic Structure.ppt

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Mass Spectrometry andIsotopic Abundances

Mass spectrum of Ne+ ions shown below.– How scientists determine the masses and

abundances of the isotopes of an element.

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The Atomic Weight Scale and Atomic Weights

If we define the mass of 12C as exactly 12 atomic mass units (amu), then it is possible to establish a relative weight scale for atoms.

– 1 amu = (1/12) mass of 12C by definition– What is the mass of an amu in grams?

Example 5-1: Calculate the number of atomic mass units in one gram.

– The mass of one 31P atom has been experimentally determined to be 30.99376 amu.

– 1 mol of 31P atoms has a mass of 30.99376 g.

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The Atomic Weight Scale and Atomic Weights

Pg 30.99376

atoms P 10 6.022g) (1.000

31

3123

Page 28: CHAPTER 05- Atomic Structure.ppt

28

The Atomic Weight Scale and Atomic Weights

– Thus 1.00 g = 6.022 x 1023 amu.– This is always true and provides the conversion factor between grams and amu.

Pamu 10 6.022 atom P

amu 30.99376

Pg 30.99376

atoms P 10 6.022g) (1.000

312331

31

3123

Page 29: CHAPTER 05- Atomic Structure.ppt

29

The Atomic Weight Scale and Atomic Weights

The atomic weight of an element is the weighted average of the masses of its stable isotopes

Example 5-2: Naturally occurring Cu consists of 2 isotopes. It is 69.1% 63Cu with a mass of 62.9 amu, and 30.9% 65Cu, which has a mass of 64.9 amu. Calculate the atomic weight of Cu to one decimal place.

Page 30: CHAPTER 05- Atomic Structure.ppt

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The Atomic Weight Scale and Atomic Weights

amu) .9(0.691)(62 weight atomic

isotopeCu 63

Page 31: CHAPTER 05- Atomic Structure.ppt

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The Atomic Weight Scale and Atomic Weights

isotopeCu isotopeCu 6563

amu) .9(0.309)(64 amu) .9(0.691)(62 weight atomic

Page 32: CHAPTER 05- Atomic Structure.ppt

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The Atomic Weight Scale and Atomic Weights

copperfor amu 63.5 weight atomic

amu) .9(0.309)(64 amu) .9(0.691)(62 weight atomic

isotopeCu isotopeCu 6563

Page 33: CHAPTER 05- Atomic Structure.ppt

33

The Atomic Weight Scale and Atomic Weights

Example 5-3: Naturally occurring chromium consists of four isotopes. It is 4.31% 24

50Cr, mass = 49.946 amu, 83.76% 24

52Cr, mass = 51.941 amu, 9.55% 24

53Cr, mass = 52.941 amu, and 2.38% 24

54Cr, mass = 53.939 amu. Calculate the atomic weight of chromium.

You do it!You do it!

Page 34: CHAPTER 05- Atomic Structure.ppt

34

The Atomic Weight Scale and Atomic Weights

amu 51.998

amu 1.2845.056 43.506 2.153

amu) 53.9390.0238(amu) 52.941(0.0955

amu) 51.941(0.8376amu) 49.946(0.0431 weight atomic

Page 35: CHAPTER 05- Atomic Structure.ppt

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The Atomic Weight Scale and Atomic Weights

Example 5-4: The atomic weight of boron is 10.811 amu. The masses of the two naturally occurring isotopes 5

10B and 511B, are 10.013

and 11.009 amu, respectively. Calculate the fraction and percentage of each isotope.

You do it!You do it! This problem requires a little algebra.

– A hint for this problem is x + (1-x) = 1

Page 36: CHAPTER 05- Atomic Structure.ppt

36

The Atomic Weight Scale and Atomic Weights

x

x

xx

xx

xx

199.0

-0.9960.198-

amu 11.009 - 10.013amu 11.009-10.811

amu 11.009-11.009 10.013

amu) (11.0091amu) (10.013 amu 10.811

isotope Bisotope B 1110

Page 37: CHAPTER 05- Atomic Structure.ppt

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The Atomic Weight Scale and Atomic Weights

Note that because x is the multiplier for the 10B isotope, our solution gives us the fraction of natural B that is 10B.

Fraction of 10B = 0.199 and % abundance of 10B = 19.9%.

The multiplier for 11B is (1-x) thus the fraction of 11B is 1-0.199 = 0.811 and the % abundance of 11B is 81.1%.

Page 38: CHAPTER 05- Atomic Structure.ppt

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The Electronic Structures of AtomsThe Electronic Structures of AtomsElectromagnetic Radiation

The wavelengthwavelength of electromagnetic radiation has the symbol

Wavelength is the distance from the top (crest) of one wave to the top of the next wave.

– Measured in units of distance such as m,cm, Å.– 1 Å = 1 x 10-10 m = 1 x 10-8 cm

The frequencyfrequency of electromagnetic radiation has the symbol

Frequency is the number of crests or troughs that pass a given point per second.

– Measured in units of 1/time - s-1

Page 39: CHAPTER 05- Atomic Structure.ppt

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Electromagnetic Radiation

The relationship between wavelength and frequency for any wave is velocity =

For electromagnetic radiation the velocity is 3.00 x 108 m/s and has the symbol c.

Thus c = forelectromagnetic radiation

Page 40: CHAPTER 05- Atomic Structure.ppt

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Electromagnetic Radiation

Molecules interact with electromagnetic radiation.– Molecules can absorb and emit light.

Once a molecule has absorbed light (energy), the molecule can:1. Rotate2. Translate3. Vibrate4. Electronic transition

Page 41: CHAPTER 05- Atomic Structure.ppt

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Electromagnetic Radiation

For water:– Rotations occur in the microwave portion of spectrum.– Vibrations occur in the infrared portion of spectrum.

– Translation occurs across the spectrum.– Electronic transitions occur in the ultraviolet portion of spectrum.

Page 42: CHAPTER 05- Atomic Structure.ppt

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Electromagnetic Radiation

Example 5-5: What is the frequency of green light of wavelength 5200 Å?

m10 5.200 Å 1

m 10 x 1 Å) (5200

c c

7-10-

1-14

7-

8

s 10 5.77

m10 5.200

m/s 10 3.00

Page 43: CHAPTER 05- Atomic Structure.ppt

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Electromagnetic Radiation

In 1900 Max Planck studied black body radiation and realized that to explain the energy spectrum he had to assume that:

1. energy is quantized

2. light has particle character

Planck’s equation is

sJ 10x 6.626 constant s Planck’ h

hc or E h E

34-

Page 44: CHAPTER 05- Atomic Structure.ppt

44

Electromagnetic Radiation

Example 5-6: What is the energy of a photon of green light with wavelength 5200 Å?What is the energy of 1.00 mol of these photons?

photon per J10 3.83 E

) s 10 s)(5.77J10 (6.626 E

h E

s 10 x 5.77 that know we5,-5 Example From

19-

1-1434-

-114

kJ/mol 231 photon)per J10 .83photons)(3 10 (6.022

:photons of mol 1.00For 19-23

Page 45: CHAPTER 05- Atomic Structure.ppt

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The Photoelectric Effect

Light can strike the surface of some metals causing an electron to be ejected.

Page 46: CHAPTER 05- Atomic Structure.ppt

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The Photoelectric Effect

What are some practical uses of the photoelectric effect?

You do it!

Electronic door openers Light switches for street lights Exposure meters for cameras Albert Einstein explained the photoelectric effect

– Explanation involved light having particle-like behavior.– Einstein won the 1921 Nobel Prize in Physics for this work.

Page 47: CHAPTER 05- Atomic Structure.ppt

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Atomic Spectra and the Bohr Atom

An emission spectrum is formed by an electric current passing through a gas in a vacuum tube (at very low pressure) which causes the gas to emit light.– Sometimes called a bright line spectrum.

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Atomic Spectra and the Bohr Atom

An absorption spectrum is formed by shining a beam of white light through a sample of gas.– Absorption spectra indicate the wavelengths of light that

have been absorbed.

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Atomic Spectra and the Bohr Atom

Every element has a unique spectrum. Thus we can use spectra to identify elements.

– This can be done in the lab, stars, fireworks, etc.

Page 50: CHAPTER 05- Atomic Structure.ppt

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Atomic Spectra and the Bohr Atom

Atomic and molecular spectra are important indicators of the underlying structure of the species.

In the early 20th century several eminent scientists began to understand this underlying structure.– Included in this list are:– Niels Bohr– Erwin Schrodinger – Werner Heisenberg

Page 51: CHAPTER 05- Atomic Structure.ppt

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Atomic Spectra and the Bohr Atom

Example 5-7: An orange line of wavelength 5890 Å is observed in the emission spectrum of sodium. What is the energy of one photon of this orange light?

You do it!You do it!

J 10375.3

m 10890.5

m/s 1000.3sJ 10626.6

hchE

m 10890.5Å

m 10 1 Å 5890

19

7

834

7-10

m 10890.5Å

m 10 1 Å 5890 7

-10

hchE

m 10890.5Å

m 10 1 Å 5890 7

-10

m 10890.5

m/s 1000.3sJ 10626.6

hchE

m 10890.5Å

m 10 1 Å 5890

7

834

7-10

Page 52: CHAPTER 05- Atomic Structure.ppt

52

Atomic Spectra and the Bohr Atom

The Rydberg equation is an empirical equation that relates the wavelengths of the lines in the hydrogen spectrum.

hydrogen of spectrumemission

in the levelsenergy theof

numbers therefer to sn’

n n

m 10 1.097 R

constant Rydberg theis R

n

1

n

1R

1

21

1-7

22

21

Page 53: CHAPTER 05- Atomic Structure.ppt

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Atomic Spectra and the Bohr Atom

Example 5-8. What is the wavelength of light emitted when the hydrogen atom’s energy changes from n = 4 to n = 2?

22 1-7

22

21

12

4

1

2

1m 10 1.097

1

n

1

n

1R

1

2n and 4n

22

21

12

n

1

n

1R

1

2n and 4n

16

1

4

1m 10 1.097

1

4

1

2

1m 10 1.097

1

n

1

n

1R

1

2n and 4n

1-7

22 1-7

22

21

12

Page 54: CHAPTER 05- Atomic Structure.ppt

54

Atomic Spectra and the Bohr Atom

m 104.862

m 10 2.057 1

1875.0m 10 1.097 1

0625.0250.0m 10 1.097 1

7-

1-6

1-7

1-7

1-6

1-7

1-7

m 10 2.057 1

1875.0m 10 1.097 1

0625.0250.0m 10 1.097 1

1875.0m 10 1.097 1

0625.0250.0m 10 1.097 1

1-7

1-7

0625.0250.0m 10 1.097

1 1-7

Notice that the wavelength calculated from the Rydberg equation matches the wavelength of the green colored line in the H spectrum.

Page 55: CHAPTER 05- Atomic Structure.ppt

55

Atomic Spectra and the Bohr Atom

In 1913 Neils Bohr incorporated Planck’s quantum theory into the hydrogen spectrum explanation.

Here are the postulates of Bohr’s theory.1. Atom has a number of definite and discrete

energy levels (orbits) in which an electron may exist without emitting or absorbing electromagnetic radiation.

As the orbital radius increases so does the energy

1<2<3<4<5......

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Atomic Spectra and the Bohr Atom

2. An electron may move from one discrete energy level (orbit) to another, but, in so doing, monochromatic radiation is emitted or absorbed in accordance with the following equation.

E E

hc h E E - E

12

1 2

Energy is absorbed when electrons jump to higher orbits.

n = 2 to n = 4 for example

Energy is emitted when electrons fall to lower orbits.

n = 4 to n = 1 for example

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57

Atomic Spectra and the Bohr Atom

3. An electron moves in a circular orbit about the nucleus and it motion is governed by the ordinary laws of mechanics and electrostatics, with the restriction that the angular momentum of the electron is quantized (can only have certain discrete values).

angular momentum = mvr = nh/2h = Planck’s constant n = 1,2,3,4,...(energy levels)

v = velocity of electron m = mass of electron

r = radius of orbit

Page 58: CHAPTER 05- Atomic Structure.ppt

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Atomic Spectra and the Bohr Atom

Light of a characteristic wavelength (and frequency) is emitted when electrons move from higher E (orbit, n = 4) to lower E (orbit, n = 1).– This is the origin of emission spectra.

Light of a characteristic wavelength (and frequency) is absorbed when electron jumps from lower E (orbit, n = 2) to higher E (orbit, n= 4)– This is the origin of absorption spectra.

Page 59: CHAPTER 05- Atomic Structure.ppt

59

Atomic Spectra and the Bohr Atom

Bohr’s theory correctly explains the H emission spectrum.

The theory fails for all other elements because it is not an adequate theory.

Page 60: CHAPTER 05- Atomic Structure.ppt

60

The Wave Nature of the Electron

In 1925 Louis de Broglie published his Ph.D. dissertation.– A crucial element of his dissertation is that electrons

have wave-like properties.– The electron wavelengths are described by the de

Broglie relationship.

particle of velocity v

particle of mass m

constant s Planck’ hmv

h

Page 61: CHAPTER 05- Atomic Structure.ppt

61

The Wave Nature of the Electron

De Broglie’s assertion was verified by Davisson & Germer within two years.

Consequently, we now know that electrons (in fact - all particles) have both a particle and a wave like character.– This wave-particle duality is a fundamental property

of submicroscopic particles.

Page 62: CHAPTER 05- Atomic Structure.ppt

62

The Wave Nature of the Electron

Example 5-9. Determine the wavelength, in m, of an electron, with mass 9.11 x 10-31 kg, having a velocity of 5.65 x 107 m/s.

– Remember Planck’s constant is 6.626 x 10-34 Js which is also equal to 6.626 x 10-34 kg m2/s2.

m 1029.1

m/s 1065.5kg 109.11

sm kg 10626.6

mv

h

11

731-

2234

m/s 1065.5kg 109.11

sm kg 10626.6

mv

h

731-

2234

Page 63: CHAPTER 05- Atomic Structure.ppt

63

The Wave Nature of the Electron

Example 5-10. Determine the wavelength, in m, of a 0.22 caliber bullet, with mass 3.89 x 10-3 kg, having a velocity of 395 m/s, ~ 1300 ft/s.

You do it!You do it!

m 1031.4

m/s 953kg 103.89

sm kg 10626.6

mv

h

34

3-

2234

m/s 953kg 1089.3

sm kg 10626.6

mv

h

3-

2234

• Why is the bullet’s wavelength so small compared to the electron’s wavelength?

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The Quantum Mechanical Picture of the Atom

Werner Heisenberg in 1927 developed the concept of the Uncertainty Principle.

It is impossible to determine simultaneously both the position and momentum of an electron (or any other small particle).– Detecting an electron requires the use of

electromagnetic radiation which displaces the electron! Electron microscopes use this phenomenon

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The Quantum Mechanical Picture of the Atom

Consequently, we must must speak of the electrons’ position about the atom in terms of probability functions.

These probability functions are represented as orbitals in quantum mechanics.

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66

The Quantum Mechanical Picture of the Atom

Basic Postulates of Quantum Theory

1. Atoms and molecules can exist only in certain energy states. In each energy state, the atom or molecule has a definite energy. When an atom or molecule changes its energy state, it must emit or absorb just enough energy to bring it to the new energy state (the quantum condition).

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The Quantum Mechanical Picture of the Atom

2. Atoms or molecules emit or absorb radiation (light) as they change their energies. The frequency of the light emitted or absorbed is related to the energy change by a simple equation.

hc

h E

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68

The Quantum Mechanical Picture of the Atom

3. The allowed energy states of atoms and molecules can be described by sets of numbers called quantum numbers.

Quantum numbers are the solutions of the Schrodinger, Heisenberg & Dirac equations.

Four quantum numbers are necessary to describe energy states of electrons in atoms.

EV8

b

equationdinger oSchr

2

2

2

2

2

2

2

2

..

zyxm

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69

Quantum Numbers

The principal quantum number has the symbol – n.n = 1, 2, 3, 4, ...... “shells”

n = K, L, M, N, ......

The electron’s energy depends principally on n .

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Quantum Numbers

The angular momentum quantum number has the symbol . = 0, 1, 2, 3, 4, 5, .......(n-1) = s, p, d, f, g, h, .......(n-1)

tells us the shape of the orbitals. These orbitals are the volume around the atom

that the electrons occupy 90-95% of the time.This is one of the places where Heisenberg’s

Uncertainty principle comes into play.

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71

Quantum Numbers

The symbol for the magnetic quantum number is m.m = - , (- + 1), (- +2), .....0, ......., ( -2), ( -1),

If = 0 (or an s orbital), then m = 0. – Notice that there is only 1 value of m.

This implies that there is one s orbital per n value. n 1

If = 1 (or a p orbital), then m = -1,0,+1.– There are 3 values of m.

Thus there are three p orbitals per n value. n 2

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Quantum Numbers

If = 2 (or a d orbital), then m = -2,-1,0,+1,+2.– There are 5 values of m.

Thus there are five d orbitals per n value. n 3

If = 3 (or an f orbital), then m = -3,-2,-1,0,+1,+2, +3. – There are 7 values of m.

Thus there are seven f orbitals per n value, n

Theoretically, this series continues on to g,h,i, etc. orbitals.– Practically speaking atoms that have been discovered or made up to this point in time only have electrons in s, p, d, or f orbitals in their

ground state configurations.

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73

Quantum Numbers

The last quantum number is the spin quantum number which has the symbol ms.

The spin quantum number only has two possible values.

– ms = +1/2 or -1/2– ms = ± 1/2

This quantum number tells us the spin and orientation of the magnetic field of the electrons.

Wolfgang Pauli in 1925 discovered the Exclusion Principle.

– No two electrons in an atom can have the same set of 4 quantum numbers.

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74

Atomic Orbitals

Atomic orbitals are regions of space where the probability of finding an electron about an atom is highest.

s orbital properties:– There is one s orbital per n level. = 0 1 value of m

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75

Atomic Orbitals

s orbitals are spherically symmetric.

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76

Atomic Orbitals

p orbital properties:– The first p orbitals appear in the n = 2 shell.

p orbitals are peanut or dumbbell shaped volumes.– They are directed along the axes of a Cartesian coordinate

system.

There are 3 p orbitals per n level. – The three orbitals are named px, py, pz.

– They have an = 1.– m = -1,0,+1 3 values of m

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77

Atomic Orbitals

p orbitals are peanut or dumbbell shaped.

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78

Atomic Orbitals

d orbital properties:– The first d orbitals appear in the n = 3 shell.

The five d orbitals have two different shapes:– 4 are clover leaf shaped.– 1 is peanut shaped with a doughnut around it.– The orbitals lie directly on the Cartesian axes or are rotated

45o from the axes.

222 zy-xxzyzxy d ,d ,d ,d ,d

There are 5 d orbitals per n level.–The five orbitals are named –They have an = 2.–m = -2,-1,0,+1,+2 5 values of m

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79

Atomic Orbitals

d orbital shapes

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80

Atomic Orbitals

f orbital properties:– The first f orbitals appear in the n = 4 shell.

The f orbitals have the most complex shapes. There are seven f orbitals per n level.

– The f orbitals have complicated names.– They have an = 3– m = -3,-2,-1,0,+1,+2, +3 7 values of m

– The f orbitals have important effects in the lanthanide and actinide elements.

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81

Atomic Orbitals

f orbital shapes

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Atomic Orbitals

Spin quantum number effects:– Every orbital can hold up to two electrons.

Consequence of the Pauli Exclusion Principle.– The two electrons are designated as having– one spin up and one spin down

Spin describes the direction of the electron’s magnetic fields.

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83

Paramagnetism and Diamagnetism

Unpaired electrons have their spins aligned or – This increases the magnetic field of the atom.

Atoms with unpaired electrons are called paramagnetic .– Paramagnetic atoms are attracted to a magnet.

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Paramagnetism and Diamagnetism

Paired electrons have their spins unaligned – Paired electrons have no net magnetic field.

Atoms with unpaired electrons are called diamagneticdiamagnetic. – Diamagnetic atoms are repelled by a magnet.

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85

Paramagnetism and Diamagnetism

Because two electrons in the same orbital must be paired, it is possible to calculate the number of orbitals and the number of electrons in each n shell.

The number of orbitals per n level is given by n2. The maximum number of electrons per n level is

2n2.– The value is 2n2 because of the two paired electrons.

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86

Paramagnetism and Diamagnetism

Energy Level # of Orbitals Max. # of e-

nn nn22 2n2

1 1 2

2 4 8

You do it!You do it!

3 9 18

4 16 32

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87

The Periodic Table and Electron Configurations

The principle that describes how the periodic chart is a function of electronic configurations is the Aufbau Principle.

The electron that distinguishes an element from the previous element enters the lowest energy atomic orbital available.

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The Periodic Table and Electron Configurations

The Aufbau Principle describes the electron filling order in atoms.

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89

The Periodic Table and Electron Configurations

There are two ways to remember the correct filling order for electrons in atoms.1. You can use this mnemonic.

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90

The Periodic Table and Electron Configurations

2. Or you can use the periodic chart .

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91

The Periodic Table and Electron Configurations

Now we will use the Aufbau Principle to determine the electronic configurations of the elements on the periodic chart.

1st row elements.

22

11

1s He

1s H

ionConfigurat 1s

11 1s H

ionConfigurat 1s

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92

The Periodic Table and Electron Configurations

2nd row elements.

•Hund’s rule tells us that the electrons will fill thep orbitals by placing electrons in each orbital singly and with same spin until half-filled. Thenthe electrons will pair to finish the p orbitals.

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93

The Periodic Table and Electron Configurations

4th row elements

119 4s Ar ArK

ionConfigurat 4p 4s 3d

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94

The Periodic Table and Electron Configurations

6102

36

510235

410234

310233

210232

110231

4p 3d 4s Ar ArKr

4p 3d 4s Ar ArBr

4p 3d 4s Ar Ar Se

4p 3d 4s Ar Ar As

4p 3d 4s Ar Ar Ge

4p 3d 4s Ar ArGa

ionConfigurat 4p 4s 3d

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95

The Periodic Table and Electron Configurations

Now we can write a complete set of quantum numbers for all of the electrons in these three elements as examples.

– Na– Ca– Fe

First for 11Na.– When completed there must be one set of 4 quantum numbers for

each of the 11 electrons in Na(remember Ne has 10 electrons)

111 s3 Ne NeNa

ionConfigurat 3p 3s

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The Periodic Table and Electron Configurations

1/2 0 0 1 e 1

m m n -st

s

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The Periodic Table and Electron Configurations

electrons s 11/2 0 0 1 e 2

1/2 0 0 1 e 1

m m n

-nd

-st

s

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98

The Periodic Table and Electron Configurations

1/2 0 0 2 e 3

electrons s 11/2 0 0 1 e 2

1/2 0 0 1 e 1

m m n

-rd

-nd

-st

s

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99

The Periodic Table and Electron Configurations

electrons s 21/2 0 0 2 e 4

1/2 0 0 2 e 3

electrons s 11/2 0 0 1 e 2

1/2 0 0 1 e 1

m m n

-th

-rd

-nd

-st

s

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100

The Periodic Table and Electron Configurations

1/2 1- 1 2 e 5

electrons s 21/2 0 0 2 e 4

1/2 0 0 2 e 3

electrons s 11/2 0 0 1 e 2

1/2 0 0 1 e 1

m m n

-th

-th

-rd

-nd

-st

s

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101

The Periodic Table and Electron Configurations

1/2 0 1 2 e 6

1/2 1- 1 2 e 5

electrons s 21/2 0 0 2 e 4

1/2 0 0 2 e 3

electrons s 11/2 0 0 1 e 2

1/2 0 0 1 e 1

m m n

-th

-th

-th

-rd

-nd

-st

s

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102

The Periodic Table and Electron Configurations

1/2 1 1 2 e 7

1/2 0 1 2 e 6

1/2 1- 1 2 e 5

electrons s 21/2 0 0 2 e 4

1/2 0 0 2 e 3

electrons s 11/2- 0 0 1 e 2

1/2 0 0 1 e 1

m m n

-th

-th

-th

-th

-rd

-nd

-st

s

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103

The Periodic Table and Electron Configurations

1/2 1 1 2 e 8

1/2 1 1 2 e 7

1/2 0 1 2 e 6

1/2 1- 1 2 e 5

electrons s 21/2 0 0 2 e 4

1/2 0 0 2 e 3

electrons s 11/2 0 0 1 e 2

1/2 0 0 1 e 1

m m n

-th

-th

-th

-th

-th

-rd

-nd

-st

s

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104

The Periodic Table and Electron Configurations

1/2 0 1 2 e 9

1/2 1 1 2 e 8

1/2 1 1 2 e 7

1/2 0 1 2 e 6

1/2 1- 1 2 e 5

electrons s 21/2 0 0 2 e 4

1/2 0 0 2 e 3

electrons s 11/2 0 0 1 e 2

1/2 0 0 1 e 1

m m n

-th

-th

-th

-th

-th

-th

-rd

-nd

-st

s

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105

The Periodic Table and Electron Configurations

electrons p 2

1/2 1 1 2 e 10

1/2 0 1 2 e 9

1/2 1 1 2 e 8

1/2 1 1 2 e 7

1/2 0 1 2 e 6

1/2 1- 1 2 e 5

electrons s 21/2 0 0 2 e 4

1/2 0 0 2 e 3

electrons s 11/2 0 0 1 e 2

1/2 0 0 1 e 1

m m n

-th

-th

-th

-th

-th

-th

-th

-rd

-nd

-st

s

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106

The Periodic Table and Electron Configurations

electron s 31/2 0 0 3 e 11

electrons p 2

1/2 1 1 2 e 10

1/2 0 1 2 e 9

1/2 1 1 2 e 8

1/2 1 1 2 e 7

1/2 0 1 2 e 6

1/2 1- 1 2 e 5

electrons s 21/2 0 0 2 e 4

1/2 0 0 2 e 3

electrons s 11/2 0 0 1 e 2

1/2 0 0 1 e 1

m m n

-th

-th

-th

-th

-th

-th

-th

-th

-rd

-nd

-st

s

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107

The Periodic Table and Electron Configurations

Next we will do the same exercise for 20Ca.– Again, when finished we must have one set of 4 quantum numbers for each of the 20 electrons

in Ca. We represent the first 18 electrons in Ca with the symbol [Ar].

220 4s Ar [Ar]Ca

ionConfigurat 4p 4s 3d

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108

The Periodic Table and Electron Configurations

1/2 0 0 4 e 19 ]Ar[

m m n

-th

s

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109

The Periodic Table and Electron Configurations

electrons s 41/2 0 0 4 e 20

1/2 0 0 4 e 19]Ar[

m m n

-th

-th

s

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110

The Periodic Table and Electron Configurations

Finally, we do the same exercise for 26Fe.– We should have one set of 4 quantum numbers for each of the 26 electrons in Fe.

To save time and space, we use the symbol [Ar] to represent the first 18 electrons in Fe

6226 3d 4s Ar Ar Fe

ionConfigurat 4p 4s 3d

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111

The Periodic Table and Electron Configurations

1/2 0 0 4 e 19 ]Ar[

m m n

-th

s

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112

The Periodic Table and Electron Configurations

electrons s 41/2 0 0 4 e 20

1/2 0 0 4 e 19]Ar[

m m n

-th

-th

s

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113

The Periodic Table and Electron Configurations

1/2 2- 2 3 e 21

electrons s 41/2 0 0 4 e 20

1/2 0 0 4 e 19 ]Ar[

m m n

-st

-th

-th

s

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114

The Periodic Table and Electron Configurations

it! doYou e 22

1/2 2- 2 3 e 21

electrons s 41/2 0 0 4 e 20

1/2 0 0 4 e 19 ]Ar[

m m n

-nd

-st

-th

-th

s

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115

The Periodic Table and Electron Configurations

1/2 1- 2 3 e 22

1/2 2- 2 3 e 21

electrons s 41/2 0 0 4 e 20

1/2 0 0 4 e 19 [Ar]

m m n

-nd

-st

-th

-th

s

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116

The Periodic Table and Electron Configurations

1/2 0 2 3 e 23

1/2 1- 2 3 e 22

1/2 2- 2 3 e 21

electrons s 41/2 0 0 4 e 20

1/2 0 0 4 e 19 [Ar]

m m n

-rd

-nd

-st

-th

-th

s

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117

The Periodic Table and Electron Configurations

1/2 1 2 3 e 24

1/2 0 2 3 e 23

1/2 1- 2 3 e 22

1/2 2- 2 3 e 21

electrons s 41/2 0 0 4 e 20

1/2 0 0 4 e 19 [Ar]

m m n

-th

-rd

-nd

-st

-th

-th

s

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118

The Periodic Table and Electron Configurations

shell d filled-half

1/2 2 2 3 e 25

1/2 1 2 3 e 24

1/2 0 2 3 e 23

1/2 1- 2 3 e 22

1/2 2- 2 3 e 21

electrons s 41/2 0 0 4 e 20

1/2 0 0 4 e 19 [Ar]

m m n

-th

-th

-rd

-nd

-st

-th

-th

s

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119

The Periodic Table and Electron Configurations

it! doYou e 26

1/2 2 2 3 e 25

1/2 1 2 3 e 24

1/2 0 2 3 e 23

1/2 1- 2 3 e 22

1/2 2- 2 3 e 21

electrons s 41/2 0 0 4 e 20

1/2 0 0 4 e 19 [Ar]

m m n

-th

-th

-th

-rd

-nd

-st

-th

-th

s

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120

The Periodic Table and Electron Configurations

1/2 2- 2 3 e 26

1/2 2 2 3 e 25

1/2 1 2 3 e 24

1/2 0 2 3 e 23

1/2 1- 2 3 e 22

1/2 2- 2 3 e 21

electrons s 41/2 0 0 4 e 20

1/2 0 0 4 e 19 [Ar]

m m n

-th

-th

-th

-rd

-nd

-st

-th

-th

s

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121

Synthesis Question

What is the atomic number of the element that should theoretically be the noble gas below Rn?

The 6 d’s are completed with element 112 and the 7p’s are completed with element 118. Thus the next noble gas (or perhaps it will be a noble liquid) should be element 118.

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122

Group Question

In a universe different from ours, the laws of quantum mechanics are the same as ours with one small change. Electrons in this universe have three spin states, -1, 0, and +1, rather than the two, +1/2 and -1/2, that we have. What two elements in this universe would be the first and second noble gases? (Assume that the elements in this different universe have the same symbols as in ours.)

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123

End of Chapter 5

The study of various spectra is one of the fundamental tools that chemists apply to numerous areas of their work.