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CHAPTER 5. The Structure of Atoms. Chapter Outline. Subatomic Particles Fundamental Particles The Discovery of Electrons Canal Rays and Protons Rutherford and the Nuclear Atom Atomic Number Neutrons Mass Number and Isotopes Mass spectrometry and Isotopic Abundance. Chapter Goals. - PowerPoint PPT Presentation

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Page 1: CHAPTER 5

1

CHAPTER 5

The Structure of Atoms

Page 2: CHAPTER 5

2

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 5

3

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 5

4

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 5

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 5

6

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.

Page 7: CHAPTER 5

7

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 5

8

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 5

9

The Discovery of Electrons

Modifications to the basic cathode ray tube experiment.

Page 10: CHAPTER 5

10

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 5

11

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.

Page 12: CHAPTER 5

12

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

Page 13: CHAPTER 5

13

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 5

14

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 5

15

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 5

16

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 5

17

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 5

18

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 5

19

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.

Page 20: CHAPTER 5

20

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 5

21

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 5

22

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

Page 23: CHAPTER 5

23

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.

Page 24: CHAPTER 5

24

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 5

25

Mass Spectrometry andIsotopic Abundances

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

abundances of the isotopes of an element.

Page 26: CHAPTER 5

26

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.

Page 27: CHAPTER 5

27

The Atomic Weight Scale and Atomic Weights

Pg 30.99376

atoms P 10 6.022g) (1.000

31

3123

Page 28: CHAPTER 5

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 5

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 5

30

The Atomic Weight Scale and Atomic Weights

amu) .9(0.691)(62 weight atomic

isotopeCu 63

Page 31: CHAPTER 5

31

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 5

32

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 5

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 5

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 5

35

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 5

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 5

37

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 = 0.801 and the % abundance of 11B is 80.1%.

Page 38: CHAPTER 5

38

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 5

39

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 5

40

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 5

41

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 5

42

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 5

43

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 5

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 5

45

The Photoelectric Effect

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

Page 46: CHAPTER 5

46

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 5

47

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.

Page 48: CHAPTER 5

48

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.

Page 49: CHAPTER 5

49

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 5

50

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 5

51

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 5

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 5

53

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 5

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.

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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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56

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

Page 57: CHAPTER 5

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 5

58

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 5

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.

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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 5

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 5

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 5

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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64

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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65

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).

Page 67: CHAPTER 5

67

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

Page 68: CHAPTER 5

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

Page 69: CHAPTER 5

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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72

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 4

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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82

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.

Page 83: CHAPTER 5

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.

Page 84: CHAPTER 5

84

Paramagnetism and Diamagnetism

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

Atoms with paired 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.

Page 86: CHAPTER 5

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

Page 87: CHAPTER 5

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.

Page 88: CHAPTER 5

88

The Periodic Table and Electron Configurations

The Aufbau Principle describes the electron filling order in atoms.

Page 89: CHAPTER 5

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.

Page 90: CHAPTER 5

90

The Periodic Table and Electron Configurations

2. Or you can use the periodic chart .

Page 91: CHAPTER 5

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

Page 92: CHAPTER 5

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.

Page 93: CHAPTER 5

93

The Periodic Table and Electron Configurations

3rd row elements 62

18

5217

4216

3215

2214

1213

212

111

3p s3 Ne NeAr

3p s3 Ne Ne Cl

3p s3 Ne Ne S

3p s3 Ne Ne P

3p s3 Ne Ne Si

3p s3 Ne Ne Al

s3 Ne Ne Mg

s3 Ne NeNa

ionConfigurat 3p 3s

52

17

4216

3215

2214

1213

212

111

3p s3 Ne Ne Cl

3p s3 Ne Ne S

3p s3 Ne Ne P

3p s3 Ne Ne Si

3p s3 Ne Ne Al

s3 Ne Ne Mg

s3 Ne Ne Na

ionConfigurat 3p 3s

42

16

3215

2214

1213

212

111

3p s3 Ne Ne S

3p s3 Ne Ne P

3p s3 Ne Ne Si

3p s3 Ne Ne Al

s3 Ne Ne Mg

s3 Ne Ne Na

ionConfigurat 3p 3s

32

15

2214

1213

212

111

3p s3 Ne Ne P

3p s3 Ne Ne Si

3p s3 Ne Ne Al

s3 Ne Ne Mg

s3 Ne Ne Na

ionConfigurat 3p 3s

2

12

111

s3 Ne Ne Mg

s3 Ne Ne Na

ionConfigurat 3p 3s

111 s3 Ne Ne Na

ionConfigurat 3p 3s

22

14

1213

212

111

3p s3 Ne Ne Si

3p s3 Ne Ne Al

s3 Ne Ne Mg

s3 Ne Ne Na

ionConfigurat 3p 3s

12

13

212

111

3p s3 Ne Ne Al

s3 Ne Ne Mg

s3 Ne Ne Na

ionConfigurat 3p 3s

Page 94: CHAPTER 5

94

The Periodic Table and Electron Configurations

4th row elements

119 4s Ar ArK

ionConfigurat 4p 4s 3d

Page 95: CHAPTER 5

95

The Periodic Table and Electron Configurations

2

20

119

4s Ar ArCa

4s Ar ArK

ionConfigurat 4p 4s 3d

Page 96: CHAPTER 5

96

The Periodic Table and Electron Configurations

it! do You Sc

4s Ar ArCa

4s Ar ArK

ionConfigurat 4p 4s 3d

21

220

119

Page 97: CHAPTER 5

97

The Periodic Table and Electron Configurations

12

21

220

119

3d 4s Ar Ar Sc

4s Ar ArCa

4s Ar ArK

ionConfigurat 4p 4s 3d

Page 98: CHAPTER 5

98

The Periodic Table and Electron Configurations

it! do You Ti

3d 4s Ar Ar Sc

4s Ar ArCa

4s Ar ArK

ionConfigurat 4p 4s 3d

22

1221

220

119

Page 99: CHAPTER 5

99

The Periodic Table and Electron Configurations

22

22

1221

220

119

3d 4s Ar Ar Ti

3d 4s Ar Ar Sc

4s Ar ArCa

4s Ar ArK

ionConfigurat 4p 4s 3d

Page 100: CHAPTER 5

100

The Periodic Table and Electron Configurations

3223

2222

1221

220

119

3d 4s Ar Ar V

3d 4s Ar Ar Ti

3d 4s Ar Ar Sc

4s Ar ArCa

4s Ar ArK

ionConfigurat 4p 4s 3d

Page 101: CHAPTER 5

101

The Periodic Table and Electron Configurations

orbitals. filled completely and filled-half with

associatedstability of measureextra an is There

3d 4s Ar ArCr

3d 4s Ar Ar V

3d 4s Ar Ar Ti

3d 4s Ar Ar Sc

4s Ar ArCa

4s Ar ArK

ionConfigurat 4p 4s 3d

5124

3223

2222

1221

220

119

Page 102: CHAPTER 5

102

The Periodic Table and Electron Configurations

5225 3d 4s Ar Ar Mn

ionConfigurat 4p 4s 3d

Page 103: CHAPTER 5

103

The Periodic Table and Electron Configurations

it! do You Fe

3d 4s Ar Ar Mn

ionConfigurat 4p 4s 3d

26

5225

Page 104: CHAPTER 5

104

The Periodic Table and Electron Configurations

62

26

5225

3d 4s Ar Ar Fe

3d 4s Ar Ar Mn

ionConfigurat 4p 4s 3d

Page 105: CHAPTER 5

105

The Periodic Table and Electron Configurations

72

27

6226

5225

3d 4s Ar Ar Co

3d 4s Ar Ar Fe

3d 4s Ar Ar Mn

ionConfigurat 4p 4s 3d

Page 106: CHAPTER 5

106

The Periodic Table and Electron Configurations

82

28

7227

6226

5225

3d 4s Ar Ar Ni

3d 4s Ar Ar Co

3d 4s Ar Ar Fe

3d 4s Ar Ar Mn

ionConfigurat 4p 4s 3d

Page 107: CHAPTER 5

107

The Periodic Table and Electron Configurations

it! do You Cu

3d 4s Ar Ar Ni

3d 4s Ar Ar Co

3d 4s Ar Ar Fe

3d 4s Ar Ar Mn

ionConfigurat 4p 4s 3d

29

8228

7227

6226

5225

Page 108: CHAPTER 5

108

The Periodic Table and Electron Configurations

reason. same y theessentiallfor

andCr like exceptionAnother

3d 4s Ar Ar Cu

3d 4s Ar Ar Ni

3d 4s Ar Ar Co

3d 4s Ar Ar Fe

3d 4s Ar Ar Mn

ionConfigurat 4p 4s 3d

10129

8228

7227

6226

5225

Page 109: CHAPTER 5

109

The Periodic Table and Electron Configurations

102

30

10129

8228

7227

6226

5225

3d 4s Ar Ar Zn

3d 4s Ar Ar Cu

3d 4s Ar Ar Ni

3d 4s Ar Ar Co

3d 4s Ar Ar Fe

3d 4s Ar Ar Mn

ionConfigurat 4p 4s 3d

Page 110: CHAPTER 5

110

The Periodic Table and Electron Configurations

110231 4p 3d 4s Ar ArGa

ionConfigurat 4p 4s 3d

Page 111: CHAPTER 5

111

The Periodic Table and Electron Configurations

it! do You Ge

4p 3d 4s Ar ArGa

ionConfigurat 4p 4s 3d

32

110231

Page 112: CHAPTER 5

112

The Periodic Table and Electron Configurations

2102

32

110231

4p 3d 4s Ar Ar Ge

4p 3d 4s Ar ArGa

ionConfigurat 4p 4s 3d

Page 113: CHAPTER 5

113

The Periodic Table and Electron Configurations

3102

33

210232

110231

4p 3d 4s Ar Ar As

4p 3d 4s Ar Ar Ge

4p 3d 4s Ar ArGa

ionConfigurat 4p 4s 3d

Page 114: CHAPTER 5

114

The Periodic Table and Electron Configurations

it! do You Se

4p 3d 4s Ar Ar As

4p 3d 4s Ar Ar Ge

4p 3d 4s Ar ArGa

ionConfigurat 4p 4s 3d

34

310233

210232

110231

Page 115: CHAPTER 5

115

The Periodic Table and Electron Configurations

4102

34

310233

210232

110231

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

Page 116: CHAPTER 5

116

The Periodic Table and Electron Configurations

5102

35

410234

310233

210232

110231

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

Page 117: CHAPTER 5

117

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

Page 118: CHAPTER 5

118

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

Page 119: CHAPTER 5

119

The Periodic Table and Electron Configurations

1/2 0 0 1 e 1

m m n -st

s

Page 120: CHAPTER 5

120

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

Page 121: CHAPTER 5

121

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

Page 122: CHAPTER 5

122

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

Page 123: CHAPTER 5

123

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

Page 124: CHAPTER 5

124

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

Page 125: CHAPTER 5

125

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

Page 126: CHAPTER 5

126

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

Page 127: CHAPTER 5

127

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

Page 128: CHAPTER 5

128

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

Page 129: CHAPTER 5

129

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

Page 130: CHAPTER 5

130

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

Page 131: CHAPTER 5

131

The Periodic Table and Electron Configurations

1/2 0 0 4 e 19 ]Ar[

m m n

-th

s

Page 132: CHAPTER 5

132

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

Page 133: CHAPTER 5

133

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

Page 134: CHAPTER 5

134

The Periodic Table and Electron Configurations

1/2 0 0 4 e 19 ]Ar[

m m n

-th

s

Page 135: CHAPTER 5

135

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

Page 136: CHAPTER 5

136

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

Page 137: CHAPTER 5

137

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

Page 138: CHAPTER 5

138

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

Page 139: CHAPTER 5

139

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

Page 140: CHAPTER 5

140

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

Page 141: CHAPTER 5

141

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

Page 142: CHAPTER 5

142

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

Page 143: CHAPTER 5

143

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