CHEM1011 Essentials of Chemistry 1A

Revision lecture
A/Prof. John A. Stride
Dalton 131 j.stride@unsw.edu.au

Questions.
question in the tutorial set 3, for number 2 about the wavelength light emitted by atomic hydrogen. Can you please explain it in the lecture? and also electron afnity. calculations on light and it's energies with use of the various equations, a) Give a valid set of four quantum numbers for each of the electrons in the nitrogen atom (in the ground state) b) Show how the Pauli principle and Hund's rule are involved in your answer to part (a) quantum numbers and atomic orbitals. electron conguration of atoms

Electromagnetic radiation: light

Is a self-sustaining oscillation of electric and magnetic elds moving through space.

Is characterised by its frequency (!) or wavelength (").

Electromagnetic radiation
units of frequency are time-1 (usually sec-1 or Hz, where 1 sec-1 = 1 Hz). units of wavelength are length (usually the SI unit: metres), with smaller units for short wavelengths: m (= 106m); nm (= 109m); (= 1010m).

Its speed of propagation depends upon the density of the substance passing the light. For vacuum, c = 2.998 x 108m s-1.

c = "#

Question?
Calculate the wavelength of electromagnetic radiation of frequency ! = 104 MHz?
Assume vacuum is the medium, so c = 2.998 x 108 m s-1.

Rearrange equation in terms of "; 2.998 $ 10 8 ms%1 Thus, " = = 2.88m 6 %1 104 $ 10 s

c "= #

visible light
The range of the electromagnetic waves that we call visible light is a very small fraction of the complete electromagnetic spectrum

ROYGBIV

visible light
The range of the electromagnetic waves that we call visible light is a very small fraction of the complete electromagnetic spectrum
Monochromatic radiation: a selection of one frequency of e.m. radiation (in practical terms, a narrow band of frequencies) which can be used for various scientific measurements etc.

Polychromatic radiation: radiation consisting of many frequencies - such as the light we receive from the sun.

ROYGBIV

E = h"

wave-particle duality

A photon with enough energy striking an atom on the metal could be absorbed, ejecting an electron, which gave a current. Only a photon with enough energy (i.e. with high enough frequency) could eject an electron from the attraction of the metal atom. This explained the threshold frequency observation). The excess energy of photons above this frequency is left over as kinetic energy on the ejected electron.

Question?
Calculate the energy of red light (wavelength = 700 nm). Compare it with blue light (wavelength 470 nm).
From the formula c = "#; c 2.998 $ 10 8 ms%1 14 -1 "= = = 4.28 $ 10 s %9 # 700 $ 10 m Then E = h" = (6.626 $ 10 %34 Js)( 4.28 $ 1014 Js) = 2.84 $ 10 %19 J For blue light (shortcut);
%34 8 %1 c (6.626 $ 10 Js)(2.998 $ 10 ms ) %19 E = h" = h $ = = 4.23 $ 10 J %9 # (470 $ 10 m)

blue light has a higher energy than red

Quantisation of energy
White (polychromatic) light passing through a gas composed of single atoms has lines or specic frequencies - removed

the lines represent the absorption spectrum of the specic gas

Quantisation of energy
A similar experiment can be performed in emission:
the same gases heated by an electrical discharge (passage of current) produces light consisting of a series of lines

emission spectrum

Quantisation of energy
The line spectra vary with the gas:

the spectra also vary with the pressure of the gas

Quantisation of energy
Recall that a bound electron has negative potential energy:

Quantisation of energy
In fact the bound electrons can occupy various discrete states Electrons can undergo transitions between these states, rather like a ball on a staircase

the hydrogen atom

$1 1 1' = RH & 2 # 2 ) " % n1 n 2 (

UV: Lyman series vis: Balmer series IR: Paschen series

the hydrogen atom

$1 1 1' = RH & 2 # 2 ) " % n1 n 2 (

The value of n for each level is called its principal quantum number. An atom in its lowest energy level ! is said to be in its ground state. Atoms can undergo transitions to higher energy levels (excited states) by being heated strongly, or by colliding energetically with other bodies. Excited states are unstable, and such states undergo transitions to lower energy levels (eventually to the ground state) by loss of energy in the form of photons.

E = h"

the hydrogen atom

$1 1 1' = RH & 2 # 2 ) " % n1 n 2 (

E = h"

Question?
One specic calculation of chemical interest is how much energy it takes to completely remove an electron from a hydrogen atom in its ground state (this is called the ionisation energy of the H atom). "Complete removal" of an electron means that the electron has been moved to the n = ! energy level.
For one H atom, "E = E final # E initial "E = #(2.18 $ 10
#18

% 1 1 ( #18 J) $ ' # = # 2.18 $ 10 J) $ (0 # 1) * ( 2 ' n2 * & final n initial )

"E = 2.18 $ 10#18 J For a mole of H atoms, the molar ionisation energy would be : "E = (2.18 $ 10#18 J) $ (6.023 $ 10 23 mole#1 ) = 1.31 $ 10 6 Jmol#1

Question: (tut. 3, Q.2)

The wavelength of light emitted by atomic hydrogen is given by the equation:

$1 1 1' = RH & 2 # 2 ) " % n1 n 2 (

Where RH is the Rydberg constant for hydrogen with the value RH = 1.096776 " 107 m-1. (a) The Lyman series in the spectrum of the hydrogen atom originate from transitions for which the lower energy level has n = 1. Calculate the wavenumber (either m-1 or cm-1), wavelength (either in nm or m) and the frequency (s-1 or Hz) of the two longest wavelength lines in the Lyman series. Indicate the region of the spectrum corresponding to these transitions.

(b)

If the electron of the hydrogen atom is raised from the lowest level (n = 1) to the energy level n = !, the electron becomes free of the atom and the H+(g) ion is produced. Calculate the energy required for this process (in J atom-1 and kJ mol-1)

The wavelength of light emitted by atomic hydrogen is given by the equation:

Question: (tut. 3, Q.2)

$1 1 1' = RH & 2 # 2 ) " % n1 n 2 (

Where RH is the Rydberg constant for hydrogen with the value RH = 1.096776 " 107 m-1. (a) The Lyman series in the spectrum of the hydrogen atom originate from transitions for which the lower energy level has n = 1. Calculate the wavenumber (either m-1 or cm-1), wavelength (either in nm or m) and the frequency (s-1 or Hz) of the two longest wavelength lines in the Lyman series. Indicate the region of the spectrum corresponding to these transitions.

The 2 longest # transitions are the lowest energy transitions: (n = 2 $ n = 1) and (n = 3 $ n = 1)

$1 1' $ 1 1' 7 1 ) = RH & ) = 8.22582 * 10 6 m#1 + 82258.2cm#1 2 # 2 ) = 1.096776 * 10 & # & %1 4 ( " %1 2 ( 1 #7 "= 6 = 121.5684 nm + 1.215684 * 10 m 3.22582 * 10 c 2.997925 * 10 8 ms #1 c = ", - , = = = 2.466039 * 1015 s#1 + 2.466039 * 1015 Hz #7 " 1.215684 * 10 m $1 1' $ 1 1' 7 1 6 #1 ) = RH & + 974912.0cm#1 2 # 2 ) = 1.096776 * 10 & # ) = 9.749120 * 10 m & % ( " 1 3 1 9 % ( 1 "= = 101.5734 nm + 1.015734 * 10 #7 m 9.749120 * 10 6 c 2.997925 * 10 8 ms #1 c = ", - , = = = 2.951486 * 1015 s#1 + 2.951486 * 1015 Hz " 1.015734 * 10 #7 m

UV

Question: (tut. 3, Q.2)

The wavelength of light emitted by atomic hydrogen is given by the equation:

$1 1 1' = RH & 2 # 2 ) " % n1 n 2 (

Where RH is the Rydberg constant for hydrogen with the value RH = 1.096776 " 107 m-1. (b) If the electron of the hydrogen atom is raised from the lowest level (n = 1) to the energy level n = !, the electron becomes free of the atom and the H+(g) ion is produced. Calculate the energy required for this process (in J atom-1 and kJ mol-1)

%1 % ( 1 1 ( 7 1 * = RH ' # = 1.096776 + 10 # 0 ' * = 1.096776 + 10 7 m#1 2 2 ' * &1 ) " &1 $ ) c c E = h, and c = ," : -, = and so E = h = 6.626068 + 10 -34 + 3.0 + 10 8 + 1.096776 + 10 7 = 2.178721 + 10 #18 J atom#1 " " #18 #1 23 2.178721 + 10 J atom = 6.022045 + 10 + 2.178721 + 10 #18 J mol#1 = 1312036 J mol#1 =1312kJ mol#1

QUANTUM MECHANICS OF THE H ATOM

solutions to the Schrdinger equation:

" = E" H

have exact analytical forms for the 1 electron H atom. the electron density at any point is given by the square of the wavefunction: 2 #

" = ""

however, the Heisenberg uncertainty principle limits the ability to know both the position and energy of a quantum particle such as an electron.

We therefore need to think about electron probability densities.

quantum numbers
principal quantum number, n
% n = 1, 2, 3, 4,., !

azimuthal (angluar mometum) quantum number, l

% l = 0, 1, 2, 3,., (n - 1)

magnetic quantum number, ml

% ml = (-l), (-l + 1),., 0,., (l - 1), (l)

spin quantum number, s

% s = +1/2 or -1/2

Question?
For an orbital with n = 3, what values of l and ml are allowed?
Values of l depend upon the n value, ranging from 0 up to n 1 in integer steps: thus l = 0, 1 and 2. In turn, the ml values are dependent upon the l values. For each l value, ml = +l,...0-l by integer steps: For l = 0, ml can only take the value of 0. For l = 1, ml takes the values ml = +1, 0 and 1. For l = 2, ml takes the values ml = +2, +1, 0, 1, and 2.

 SHELL

quantum numbers

A set of orbitals with the same value of n are called a shell. For the hydrogen atom, with its single electron, all orbitals in the same shell have the same energy. ORBITAL SYMBOLS A set of orbitals with the same n and l is called a sub!shell. For convenience these are labelled with letters:
If l = 0, the orbitals are called s orbitals, If l = 1, the orbitals are called p orbitals, If l = 2, the orbitals are called d orbitals, If l = 3, the orbitals are called f orbitals.

Orbitals are labelled with their principal quantum number, n, followed by the orbital symbol (equivalent to l). e.g. a "2s" orbital has n = 2 and l = 0.

s orbitals
(l = 0)
s orbitals are spherically symmetric

the 1s orbital has a maximum electron density probability close to the nucleus The 2s orbital is also spherically symmetric, but it has only a small peak of electron density close to the nucleus, then a node of zero density, followed by its main peak of electron density at a greater distance.
The main peak of electron density of the 2s orbital is further from the nucleus than the 1s peak, so a 2s electron would have a higher energy than a 1s electron. For the hydrogen atom, the principal quantum number is a good indicator of electron energy.

# RH & %E = " 2 ( $ n '

p orbitals
(l = 1) Each p orbital consists of two lobes of electron density on opposite sides of the nucleus, with a nodal plane (zero electron density) between the lobes. Since a p orbital has l = 1, ml can have the values of +l, 0 and l, thereby giving rise to the three p orbitals: px, py and pz.
The three p orbitals have their lobes at right angles to one-another and can be pictured to lie along a set of x, y, z Cartesian axes.

d orbitals
(l = 2)
d orbitals come in sets of 5, since d orbitals have l = 2, which gives the values of ml = +2, +1, 0, 1 and 2, (i.e. ve possible values). Unlike the p orbitals, the d orbitals are not simple 90 image rotations of one-another.

Four of them consist of four lobes of electron density arranged in a quadrant about the nucleus, with two nodal planes between the lobes. Of these, one has its four lobes along the x and y axes of a set of Cartesian axes. Relative to this orbital, the other three have their lobes between the axes, in each of the planes dened by the pairs of axes. The other d orbital has just two main opposed lobes of density along the z axis, with a small torus of density at the waist.

atomic orbitals
atoms can absorb energy (photons) to promote electrons to excited states the Coulombic attraction between nucleus & electrons lead to a contraction of shells with increasing nuclear charge

multi-electron atoms
the electrons around a multi-electron atom repel oneanother in a complicated way meaning that it is difcult to obtain analytical solutions to the Schrdinger equation. a useful approximation is that the orbitals resemble those of the hydrogen atom two factors come in to play in these atoms:
increased nuclear charge electron-electron repulsions % shielding

multi-electron atoms

electronic shielding
Shielding does not affect the electrons of an outer shell equally.
The s electrons of an outer shell have one or more small lobes of density close to the nucleus (inside the region of shielding electrons), and thus are less affected by shielding. This effect is smaller for p orbitals (l = 1) and progressively less for d (l = 2) and f (l = 3) orbitals.

electronic shielding

To summarise, the degree of "penetration" to the nucleus is s > p > d > f. As a result of the off-setting of shielding by different amounts of penetration, the energies of orbitals in each shell follow the order s < p < d < f.

orbital lling
orbitals are lled from the lowest energy levels up.. a simple way to remember the ordering:

Question
a) Give a valid set of four quantum numbers for each of the electrons in the nitrogen atom (in the ground state) b) Show how the Pauli principle and Hund's rule are involved in your answer to part (a)
Nitrogen has the ground state electronic configuration: 1s22s22p3: 1s electrons: n = 1, l = 0, ml = 0, s = +1/2 & -1/2 2s electrons: n = 2, l = 0, ml = 0, s = +1/2 & -1/2 2p electrons: n = 2, l = 1, ml = -1, 0, +1, s = +1/2 (for each of the 3 electrons) Pauli Principle: no more than 2 electrons in each orbital each of the s obitals has an occupancy of 2, despite being lower in energy than the 2p orbitals. Hunds Rule: maximise the multiplicity when filling orbitals the electrons in the 2p orbitals populate each of the px, py & pz with one electron (3 values of ml) rather than 2 electrons entering any one

GOOD LUCK!