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Office: Dept. of Chemistry, CAS, CLSU E-mail: chemistjoel2004 @yahoo.com Consultation Hours: Monday
The Course
Prerequisite Chemistry 250/260
Resources Physical Chemistry By : P.W.Atkins, Alberty, Levine, Ball, Laidler, Castillan Physical Chemistry : A Molecular Approach By. D. Mc Quarrie Lectures (principles, procedures, interpretation, tricks, insight) Homework problems and solutions
Course Planner
o o o o
Material covered in lectures. What to focus on or review. What to study from the book. Homework assignments. Questions for further thinking.
Grading Policy
Homework 10% (Generally, chapter assignment)
Quiz
Exams
40 %
50 %
Important Notes: Determination of the or frequency of radiation is done by means of a devise known as spectrometer. All electromagnetic radiation travel with the same velocity and may differ in their wavelength and frequency. The velocity of an electromagnetic wave (light) is found to be constant and independent of the medium in which the wave travels ( electromagnetic waves do not require any medium of propagation)
Atomic Spectra
these are line spectra shown by atoms of elements the spectra of elements are dependent upon the nature of the radiations emitted. Important Notes: 1.) Each line in the spectrum is having a characteristic frequency therefore it will have a definite energy. e.g. Hydrogen Spectrum = consists of a number of discrete lines in the visible and ultraviolet region 2.) The change in the transition state corresponds to the amount of energy absorbed
Atomic Spectra
H atom absorbs only specific 1885 J.J. Balmer (visible light) 1886 Rydberg (u.v light) 1908 Ritz ( Infrared) Balmer showed that for the visible lines of hydrogen, a plot of v (frequency) vs 1/n2 gave a straight line. Rydberg = who put forward that the wavenumber (cm-) of any line of the hydrogen spectrum can be represented as a difference of two terms, one of which is constant and the other varies throughout the series.
Sample Problem
Calculate the wavelength of the second line in the Paschen series, and show that this line lies int the near infrared, that is, in the infrared region near the visible Ans: = 1.282 x 10-4 cm =1282 nm
1859: Kirchoff
Same behavior of radiation emitted/absorbed for different materials this implies something fundamental about radiation 1879: Stefan Boltzmann Law = aT4 the total energy density is proportional to the fourth power of the temperature. (based from the area of the graph the area increases with the fourth power of the temperature).
Justification: The electromagnetic field inside the container has a definite total energy , which increases as the temperature.
The total energy density is the total energy divided by the volume of the interior of the container.
Limitations
Rayleigh Jeans formula is quite successful at long and low v, but it fails badly at high v and short . This failure is called UV breakdown/ catastrophe (leads to infinite energy). The frequency increases as the radiation enters the ultraviolet region, the divergence in the radiant energy density as v2 (frequency) was termed the ultraviolet catastrophe.
Planck Distribution d= d Where: ( ,t) = (8hc/5) (d/ ehc/kT - 1) ( v,t) = (8hv3 /c3) (dv / ehv/kT - 1)
Important Notes: 1.) Planck formula reduces to the Rayleigh Jeans Law for long radiation.
2.) Planck distribution also accounts for the Stefan Boltzmann and Wien Law
Weins Law
By looking at d/ d = 0
Sample Problem
1.)Equation ( v,t) = (8hv3 /c3) (dv / ehv/kT - 1) expresses Plancks radiation law in terms of frequency. Express Plancks radiation law in terms of . 2.) a.) Derive the Stefan Boltzmann and Wein equations using Plancks distribution of blackbody radiation. b.) Account that Plancks formula reduces to the Rayleigh Jeans law for long wavelength of radiation.
1907: Einstein
Heat Capacity of Solids According to Classical Mechanics The mean vibrational energy of each atom of a solid is 3 KT For solid composed of N atoms, the total vibrational energy : Ev = 3NkT The contribution of the vibrational energy to the molar internal energy UM = 3NkT = 3 RT The molar heat capacity at constant volume is
Cvm = (Um/ T)V = 3R (Law of Dulong and Petit Limitations of Dulong and Petits law
deviations were observed when applied to measure heat capacities at low temp.
Einstein Formula
accounts for the decrease of heat capacity at low temperature. Assumption: Each atom oscillates about its equilibrium position with a single frequency (v).
Assumptions
1.) Force of attraction between the electron and the nucleus 2.) Centrifugal force experienced by the electron ( under the influence of which the electron tends to fly away from the nucleus) 3.) The electron does not fall into the nucleus 4.) Incorporating Bohrs quantum condition 5.) When the electron is excited from n1 to n2 having E1 and E2.
Sample Problem
Find the radius of the Bohr orbit for the most stable state (minimum energy) of a hydrogenic atom. Ans: An electron moving about a nucleus of charge ze in a circular orbit has an angular momentum.
e.g. why the momentum of the electron should have only those values which are integral multiple of h/2 and why not h/3.
3.) could not explain the reason why atoms should combine to form chemical bonds.
Photoelectric Effect
1905 : Einstein This effect is due to the ejection of electrons from metals when they are exposed to UV light. Essential Features of the Photoelectric effect i.) No electrons are ejected, regardless of the intensity of the radiation, unless its frequency exceeds a threshold value, which is a characteristic of a metal ii.) The kinetic energy of the ejected electrons varies linearly with the frequency of the incident radiation iii.) Even at low light intensities, electrons are ejected immediately if the frequency is above threshold.
Sample Problem
When Lithium is irradiated with light, the kinetic energy of the ejected electron is 2.935 x 10-19J for = 300.0 nm. Calculate the threshold frequency and the work function of lithium from these data. Ans. Vo = 5.564 x 1014 Hz = 3.687 x10 -19 J = 2.301 eV
Compton Effect
The photons were observed to be scattered at all angles by the electrons of the scattering material.
Arthur Compton = investigated the scattering of monochromatic x -rays by a target such as a piece of graphite. The scattered beam consisted of a radiation of 2 different wavelength's.
Quantization of Momentum
Assumptions: i.) the electron wave is moving in a circle ii.) the motion of the electron should be in phase ( so that the electron will continuously move in a circular orbit) Circumference of circular orbit = integral multiple of its wavelength 2r = n where : r = radius of the orbit = wavelength of electron wave
Quantization of Momentum
From de Broglie relationship = 2r / n Comparing the two equations mvr = nh / 2 Bohr Postulate mvr = angular momentum of the electron Standing wave = the distance between two points will not change with time Only integral numbers of s will form a standing waves
Louis de Broglie
1924: Louis de Broglie Concluded that energy is associated with both light and matter (particle) Electrons have both particle and wave properties ( every particle can be considered to have an associated and wave properties) = h/mc = h/mv de Broglie equation
Sample Problem
Estimate the wavelength of electrons that have been accelerated from rest through a potential difference of 1.00 kV Hint: EK = mev2 = p2/2me Where: p = mev The energy acquired by electron that falls through a potential difference is given by: e x p = 2mee and = h / p Ans. 3.88 x 10-11m
p . x /2 or h/4
Likewise for simultaneous measurements of E and time
E . t /2
Sample Problem
Calculate the uncertainty in the position of a baseball(5.0 oz) thrown at 90mph if we measure its momentum to a millionth of 1.0 %. Ans. p = 5.6 kgm/s; 1mile = 1610 m; 1lb = 16oz x = 1.2 x 10-26 m
Quantum Mechanics
The basic concept is energy is quantized e.g. spectrum of a solution Basically statistical in nature ( probabilistic approach) = knowing the state, we cannot predict the result of a position measurement with certainty, we can only predict the probabilities of various possible results Associated with each physical observable ( position, momentum and energy) is a mathematical operator. From these operator we can predict the behavior of a physical system