Atomic Structure

Abstract Model: A theory/picture that we have which we cannot directly observe. We produce evidence that supports the theory and we modify it or get rid of it gradually. Atom: Fundamental particle, which cannot be divided. Atoms are made of sub-atomic particles:

Name Proton Neutron Electron

Symbol P+ N0 e-

Position Nucleus Nucleus Orbiting nucleus

Relative charge +1 0 -1

Relative Mass 1 1 510-4

Relative (compared to each other) because actual volumes are tiny and unwieldy (hard to manipulate) Actual charge e-: 1.610-9 C Actual mass p+: 1.610-24 g

Z= Atomic number = Proton Number

A= Mass Number = Relative Atomic Mass = Molar Mass = Nucleon Number = No. of Protons + Neutrons

For a neutral atom, No. p+ = No. e-. No. n0= A-Z

Most mass numbers are decimals because the number represents the average mass of all the isotopes in existence (according to their relative abundance)

Isotopes: Atoms of the same element but with different masses. They are atoms with equal No. of protons but different No. of neutrons. Some isotopes are unstable and the nuclei will break apart. Unstable= radioactive. These are radioactive. Radio isotopes emit charged particles [,] or energy wave [] Chemical properties of isotopes are the same because they are the same element. Physical properties will be slightly different due to different masses producing different amounts of attraction, which will affect things like melting point, and rate of diffusion. Uses of isotopes When unstable isotopes break down, they emit radiation. This can be used for: Nuclear power generation. To check for pipe leaks: By adding radioisotopes to the inside of a container, none should escape. If the giger counter detects any radioactivity outside they container, then theres a leak. This is used on gas/petrol pipes. Sterilizing: gamma rays kill bacteria, so they can be used to sterilize disposable lab equipment. Carbon dating: bodies contain carbon-14 from food. When we die, we stop eating, so the carbon-14 starts decaying. From that, the amount of radioactivity can be measured to find the bodys age.

Mass Spectrometer Mass spectrometers are used to detect the mass of positive ions. We can find out the proportions of different isotopes of an element. Identifying unknown substances: Stage 1 Vaporization: the sample must be heated and injected into the spectrometer as a gas. Stage 2- Ionization: A high-energy beam strips e- electrons from the atom/molecule/molecular fragments, giving them a 1+ charge. Stage 3- Acceleration: The +ions are accelerated towards a charged plate. Some pass through a small hole in the plate, producing a fine beam of +ions.

Stage 4- Deflection: Because a charged particle is deflected in a magnetic field, we use a varying magnetic field to make different mass ions hi the detector. A heavier mass will need a stronger magnetic field to deflect it to the deflector. Stage 5- Detection: When ions hit the detector a current is measured. The data collected will be plotted on a chart (mass spectrum) Relative abundance is related to the current measured by the detector. m/e / m/z = mass: charge ratio .Since mass is equal to 1+, this is equal to the mass of the ion.

Figure 1

The mass spectrum minimizes higher changed ions as this would cause confusion: A peak at 32 could be a 1+ ion, mass 32 Or a 2+ ion, mass 64 Or a 3+ ion, mass 96

Using Mass Spectrometer Data Example: Germanium The mass spectrum shows 5 peaks corresponding to five isotopes. Find the Ar. Relative Mass 70 72 73 74 76 The percentages add up to 100% Ar of Ge = = 72.5
( ) ( ) ( ) ( ) ( )

% Abundance 20.5 27.4 7.8 36.5 7.8

Question: Silicon gives the following mass spec data. Find the Ar. Mass 23 29 30 Relative Abundance 25.76 1.45 0.9

Here, the relative abundance needs to be converted to a percentage first. Total relative abundance: 28.11 1. 2. 3. Mass 23 29 30 % Abundance 91.64 5.16 3.2

Ar of Silicon:

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Question: Calculate to two decimal places the actual percentage of chlorine-35 in naturally occurring chlorine. ( ) ( ( ))

Electron Arrangement Shells equate to energy levels, principal quantum numbers. Shell 1= Principal quantum No.1, etc Principal quantum No.1 takes 2 ePrincipal quantum No.1 takes 8 ePrincipal quantum No.1 takes 18 eOn the periodic table, shell No. = Rows The lower shells have lower energy so they get filled first. Evidence for electron shells Emission Spectrum Electrons shells= principal quantum numbers = a fixed energy level. Electromagnetic spectrum: v= f .as frequency increases, wavelength () decreases. Higher frequency waves have higher energy. E= Hf H= Plancks constant (6.63 10-39 Js) If we look at the light emitted from an elements flame through a spectrometer (prism) we do not see a continuous spectrum but discreet lines of different colours (frequencies). This is due to excited electrons losing energy in the form of light as they move back to a lower energy level. The discrete frequencies tell us that electrons can only exist at specific energies, which we call principal quantum numbers or e- shells. A higher frequency emission = larger loss of energy = movement from a higher energy level. The higher frequency emissions converge (get close together) which tells us that the higher principal quantum numbers converge. Ie- the fourth shell is closer in energy to the 3rd shell than the 3rd is to the second. The visible light emissions are due to e- transitions back to n=2. Transitions to n=1 are in the ultraviolet range. Transitions to n=3 re in the infrared range.

More Evidence for Electron Arrangement Ionization energies: energy required to remove one electron from an atom in its gaseous state. 1st ionization energy:

This is the enthalpy change to remove a mole of electrons from a mole of gaseous atoms. The 1st electron to be removed will be the easiest to remove. (ie- from the outer shell/ last principal quantum number)

kemkorner.blogspot.com (Figure 2)

From the ionization graph above, we observe the following: 1- the more e- are in the outer shell, the larger the 1st ionization energy. This is because the nuclear (+) charge is increasing and is more strongly attracting the electrons. Therefore, the first ionization energy increases. 2- Lis 1st ionization energy is lower than Hes. This tells us that Lis e- is being taken from a different shell than He. Because Lis 1st ionization energy is lower than Hs, we can assume that the 2nd shell is further away from the nucleus than the 1st shell.

3- The graph gives evidence for n1= 2en2= 2en3= 8eHydrogens first ionization energy is low since one proton attracts one electron. In helium, two protons attract two electrons. Successive ionization energies

http://www.dorjegurung.com/ (Figure 3)

The graph above shows electrons being removed from a potassium atom. From it, we can observe that the 1st e- is taken from the outer shell. E-2-9 are from the next shell in, e- 10-17 (8e-) are from a shell further in, and 18 19 are rom the 1st shell. Orbitals Figure 3 gives evidence more complex than shells. Shells are further divided into subshells (orbitals) 1st quantum Number Shell Number (Principal Quantum Number 2nd quantum Number Orbital Type (s,p,d,f) 3rd quantum Number Which p,d, or f orbitals the e- is in. 4th quantum Number clockwise or anti-clockwise e- spin

Pauli said only 1 e- in an atom can have the same set of 4 quantum numbers. Because e-s can spin in 2 ways, each orbital can take up to 2e-. An orbital is a volume of space where there is a 90% chance of finding an eat a particular energy. We cannot exactly know the position of an e- at a particular time. Shell 1- 2e- in S orbital. Shell 2- 8e- (2e- in S orbital, 6e- in 3P orbitals) Shell 3- 18e- 2e- in S orbital, 6 in 3p orbitals, 10 in s p orbitals. Shell 4- 32e- 2 in S orbital, 6 in 3P orbitals, 10 in S D orbitals, 14 in 7 f orbitals.

Figure 4: faculty.njcu.edu

Evidence for Orbitals- Ionization energy The 1st ionization energy for B is lower than for Be. The 1st ionization energy for O is lower than for N. If all the e- in a shell had the same energy we would except all 1st ionization energies to increase smoothly from Li to Ne. B and Be- Bes outer shell e-s are in the 2s orbital. B has 2e- in the 2s and 1 in a slightly higher energy orbital, a 2p orbital. It takes slightly less energy to remove a 2p electron than a 2s electron. N and O N has e-s in shell 2 (2e- in 2s and 3e- in 2p (1 in px, 1 in py, 1 in pz)

O has 1 more e- which goes into 1 of the p orbitals to make the orbital full. The e-s in the full orbital spin in opposite directions, which reduces but does not remove repulsion. The repulsion means less energy is needed to remove that e-. Aufbam Principle Aufbam = building up. Ie- in what order e-s are put into orbits.

figure 5: spiff.rit.edu Figure 5 shows that 4s is filled before 3d. 4s is slightly lower in energy that 3d

Figure 6: sparknotes.com

The order in which orbitals are filled is the following: 1s,2s,2p,3s,3p,4s,3d,4p,5s,4d,5p P orbitals in a shell have equivalent energy. D orbitals in a shell have equivalent energy.

Filling up produces the lowest energy situation for the number of electrons. However, the arrangement does not apply to: Cr, Cu, Mo, and Ag In the specified elements, less energy is needed to partially fill all of the 4s and 3d orbitals. [ ] not [ ]

here, less energy is needed to completely fill the 3rd shell.

Ions and Orbitals When e-s start to appear in the d orbitals, the orbitals energy lowers to below that of the S orbital. Due to this, the first e-s to be taken when a +ion is formed will be from the 4s, not the 3d orbital. Hunds rule of maximum multiplicity suggests that electron pairing is unfavorable, and that electrons fill up in parallel before pairing up. Before two electrons occupy an orbital in a shell, other orbitals in the same shell must first each contain one electron. The electrons in a shell will have a parallel spin before the shell starts filling up with opposite spin electrons after an orbital has two electrons. Due to this, the maximum number of unpaired electrons is assured when filling up atomic orbitals. Filling order: 1s,2s,2p,3s,3p,4s,3d,4p,5s,4d,5p Removing order: 5p,5s,4d,4p,4s,3d,3p,3s,2p,2s,1s