Today I bought the two books "Solutions of Concepts of Physics" containing solutions of problems in given in H C Verma's Books.
I am yet to use them but I recommend those books for purchase by JEE aspirants.
They are prepared by Govind Verma and published by Raj Publications, Darya Ganj, New Delhi 110002
One should try to do problems in the book and after spending some set time, should see the solution, if not able to do the problem.
COMPANION SITES: www.iit-jee-chemistry.blogspot.com, www.iit-jee-maths.blogspot.com. A google search facility is available at the bottom of the page for searching any topic on these sites.
Sunday, October 26, 2008
Monday, October 20, 2008
Zeroth Law of Thermodynamics
Zeroth law of thermodynamics
If two bodies A and B are in thermal equilibrium and A and C are also in thermal equilibrium then B and C are in also in thermal equilibrium
All bodies in thermal equilibrium are assigned equal temperature.
Heat flows from the body at higher temperature to the body at lower temperature
If two bodies A and B are in thermal equilibrium and A and C are also in thermal equilibrium then B and C are in also in thermal equilibrium
All bodies in thermal equilibrium are assigned equal temperature.
Heat flows from the body at higher temperature to the body at lower temperature
Saturday, October 18, 2008
Measurment Procedures - Ch. 27 Specific Heat Capacities of Gases
Determination of Cp of a gas
Regnault’s apparatus is used to measure Cp of a gas.
It has an arrangement to send gas through a pipe where in two manometers measure the pressure at two point and in between there is an adjusting screw to change the rate of flow. As the gas is flowing through this arrangement, adjusting screw is changed to maintain a constant difference of pressure between two manometers and this ensures that gas is at constant pressure when it is flowing through the calorimeter. This gas flows through an oil bath tank wherein it is given heat and then flows through the calorimeter wherein it gives out heat.
Observations
W = the water equivalent of the calorimeter with the coil
M = mass of water in the calorimeter
θ1 = temperature of the oil bath which gives heat to the gas.
θ2 = initial temperature of water in calorimeter
θ3 = Final temperature of water in calorimeter
n = amount of the gas (in moles) passed through the water
s = specific heat capacity of water
Cp of a gas. = (W + m) s (θ3 - θ2)/[n (θ1 – (θ2+ θ3)/2]
Determination of n = amount of the gas (in moles) passed through the water
It depends on the levels of mercury in the manometer attached to gas tank. If the difference in levels of the manometer is h and the atmospheric pressure (separately measured) is equal to a height H of mercury. The difference h is noted at the start of the experiment and at the end of the experiment. The pressure of the gas varies between p1 = H+h at the beginning to p2 = H+h at the end. Under the assumption of ideal gas
p1V = n1RT and p2V = n2RT
n is equal to n1 – n2 = (p1 - p2)V/RT
Determination of Cv of a gas
Joly’s differential steam calorimeter is used to measure Cv of a gas. The arrangement has two hollow copper spheres attached to two pans of a sensitive balance. In one of the spheres the gas for which Cv is to be measured is filled. At the start the temperature of the steam chamber without any steam is noted. It is the temperature of the gas at the beginning (θ1). Steam is sent through the steam chamber in which these two hollow spheres are there. Steam condenses on the hollow spheres and it collected in the pans attached to the hollow spheres. More steam condenses on the sphere having gas in it. After steady state conditions are reached temperature measurement is taken. This the final temperature of the gas.
Observations
m1 = the mass of gas taken or filled in the hollow sphere
m2 = the mass of extra steam condensed on the pan of the sphere having gas
θ1 = the temperature of the gas at the beginning
θ2 = the temperature of the gas at the end
L = Specific latent heat of vaporization of water.
M = molecular weight of the gas
Cv = Mm2L/[m1(θ1 – θ2)]
Regnault’s apparatus is used to measure Cp of a gas.
It has an arrangement to send gas through a pipe where in two manometers measure the pressure at two point and in between there is an adjusting screw to change the rate of flow. As the gas is flowing through this arrangement, adjusting screw is changed to maintain a constant difference of pressure between two manometers and this ensures that gas is at constant pressure when it is flowing through the calorimeter. This gas flows through an oil bath tank wherein it is given heat and then flows through the calorimeter wherein it gives out heat.
Observations
W = the water equivalent of the calorimeter with the coil
M = mass of water in the calorimeter
θ1 = temperature of the oil bath which gives heat to the gas.
θ2 = initial temperature of water in calorimeter
θ3 = Final temperature of water in calorimeter
n = amount of the gas (in moles) passed through the water
s = specific heat capacity of water
Cp of a gas. = (W + m) s (θ3 - θ2)/[n (θ1 – (θ2+ θ3)/2]
Determination of n = amount of the gas (in moles) passed through the water
It depends on the levels of mercury in the manometer attached to gas tank. If the difference in levels of the manometer is h and the atmospheric pressure (separately measured) is equal to a height H of mercury. The difference h is noted at the start of the experiment and at the end of the experiment. The pressure of the gas varies between p1 = H+h at the beginning to p2 = H+h at the end. Under the assumption of ideal gas
p1V = n1RT and p2V = n2RT
n is equal to n1 – n2 = (p1 - p2)V/RT
Determination of Cv of a gas
Joly’s differential steam calorimeter is used to measure Cv of a gas. The arrangement has two hollow copper spheres attached to two pans of a sensitive balance. In one of the spheres the gas for which Cv is to be measured is filled. At the start the temperature of the steam chamber without any steam is noted. It is the temperature of the gas at the beginning (θ1). Steam is sent through the steam chamber in which these two hollow spheres are there. Steam condenses on the hollow spheres and it collected in the pans attached to the hollow spheres. More steam condenses on the sphere having gas in it. After steady state conditions are reached temperature measurement is taken. This the final temperature of the gas.
Observations
m1 = the mass of gas taken or filled in the hollow sphere
m2 = the mass of extra steam condensed on the pan of the sphere having gas
θ1 = the temperature of the gas at the beginning
θ2 = the temperature of the gas at the end
L = Specific latent heat of vaporization of water.
M = molecular weight of the gas
Cv = Mm2L/[m1(θ1 – θ2)]
Friday, October 17, 2008
ch. 25 Calorimetry - Laws and Theories
Principle of Calorimetry
Neglecting any heat exchange with the surroundings, the principle of calorimetry states that the total heat given by the hot objects equals the total heat received by the cold objects.
Mechanical equivalent of heat
W = JH
Neglecting any heat exchange with the surroundings, the principle of calorimetry states that the total heat given by the hot objects equals the total heat received by the cold objects.
Mechanical equivalent of heat
W = JH
Monday, October 13, 2008
Saturated vapour pressure - July Dec Revision
When we place an open flask with a liquid in a closed jar, after sufficient time, volume of the liquid becomes constant. We know that liquid evaporates, but at this point in time, when volume of liquid is constant, we have to interpret that rate of transformation from liquid to vapour equals the rate of transformation from vapour to liquid.
If some vapour from outside is injected into the space above the liquid in the jar, we observe that the volume of liquid will increase. That means more vapour is getting transformed into liquid.
When a space actually contains the maximum possible amount of vapour, the vapour is said to be saturated or it is called saturated vapour. If the amount of vapour in a space is less than the maximum possible, the vapour is called unsaturated vapour.
Saturated vapour increases with temperature. At higher temperature, the space contains more vapour. This is because more liquid molecules escape from liquid surface at higher temperatures.
The pressure exerted by a saturated vapour is called saturated vapour pressure. As a higher temperature more amount of vapour is there of a liquid, saturated vapour pressure is also higher at higher temperatures for a substance. Even into an empty jar, as vapour increases more and more, and pressure increases above the SVP, vapour starts condensing and liquid forms. This is as per definition of vapour. A vapour can be transformed into a liquid at a constant temperature by increasing pressure.
In the atmosphere around us air which is mixture of nitrogen and oxygen and water vapour are mixed with each other. If a given volume air contains maximum amount of vapour possible, the air called saturated with water vapour.
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If some vapour from outside is injected into the space above the liquid in the jar, we observe that the volume of liquid will increase. That means more vapour is getting transformed into liquid.
When a space actually contains the maximum possible amount of vapour, the vapour is said to be saturated or it is called saturated vapour. If the amount of vapour in a space is less than the maximum possible, the vapour is called unsaturated vapour.
Saturated vapour increases with temperature. At higher temperature, the space contains more vapour. This is because more liquid molecules escape from liquid surface at higher temperatures.
The pressure exerted by a saturated vapour is called saturated vapour pressure. As a higher temperature more amount of vapour is there of a liquid, saturated vapour pressure is also higher at higher temperatures for a substance. Even into an empty jar, as vapour increases more and more, and pressure increases above the SVP, vapour starts condensing and liquid forms. This is as per definition of vapour. A vapour can be transformed into a liquid at a constant temperature by increasing pressure.
In the atmosphere around us air which is mixture of nitrogen and oxygen and water vapour are mixed with each other. If a given volume air contains maximum amount of vapour possible, the air called saturated with water vapour.
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Thursday, October 9, 2008
Declination
A plane passing through the geographical poles(that is axis of rotation of the earth) and a given point P on the earth’s surface is called the geographical meridian at the point P. The plane passing through the geomagnetic poles (dipole axis of the earth) and the point P is called the magnetic meridian at the point P.
The angle between the magnetic meridian and the geographical meridian at a point is called the declination at that point.
Navigators use a magnetic compass needle to locate direction. The needle stays in equilibrium when it is in magnetic meridian. For finding the true north, navigators have to use declination and arrive at the direction of true north.
Chapter permanent magnets
Presently updating revision points and formula revision sheets of all chapters. Planning to complete all chapters by month end.
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The angle between the magnetic meridian and the geographical meridian at a point is called the declination at that point.
Navigators use a magnetic compass needle to locate direction. The needle stays in equilibrium when it is in magnetic meridian. For finding the true north, navigators have to use declination and arrive at the direction of true north.
Chapter permanent magnets
Presently updating revision points and formula revision sheets of all chapters. Planning to complete all chapters by month end.
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Saturday, October 4, 2008
Bohr’s Model and Physics of the Atom - July-Dec Revision
Revision - Points of the chapter
Early Atomic Models
The idea that all matter is made of very small indivisible particles is very old.
Robert Boyle’s study of compression and expansion of air brings out the idea that air is made of tiny particles with lot of empty space between the particles.
The smallest unit of an element which carries all the properties of the element is called an atom.
Experiments on discharge tube, measurement of e/m by Thomson etc. established the existence of negatively charged electrons in the atoms.
Because atoms are electrically neutral, a search for the positive charge inside the atom was started.
Thomson’s Model of the atom
Thomson (1898) suggested that the atom is a positively charged solid sphere in which electrons are embedded in sufficient number to create a neutral atom. This model of the atom could explain why only negatively charged particles are being emitted when a metal is heated. This model was also useful to explain the formation of ions and ionic compounds.
Lenard’s Suggestion
Lenard observed that cathode rays are pssing through thin material without any deviation. According to him, this was so because, there is a lot of empty space in atoms. Hence the positive charged particles are also tiny like electrons.
Rutherford’s Model of the Atom
Rutherford experimented with alpha rays or particles. When he bombarded gold foils with alpha particles, Many went without deviation, some had some deviation and some were deflected by more than 90 and came back. Hence he made a conclusion that there was a particle with a mass equivalent to alpha particle inside the atom. The mass of an atom is concentrated in this particle.
The size of this particle was also estimated by Rutherford. Its linear size is 10 fermi ( 1 fermi is equal to 1 femtometre = 10^-15 m).
Rutherford proposed that the atom contains a positively charged tiny particle called nucleus. It contains the entire mass of the atom. Outside this nucleus, at some distance, electrons move around. The positive of charge of nucleus is exactly equal to the negative charge of the electrons of the atom.
Because electrons are very very light compared to the nucleus, due to heat only electrons come out.
Movement of electrons is to brought in and the coulomb force between the nucleus and the electron is assumed to provide only centripetal force to make the electron rotate in a circular motion.
Hydrogen Spectra
If hydrogen gas is enclosed in a sealed tube and heat to high temperatures, it emits radiation. If this radiation is passed through a prsim, components are different wavelengths get deviated by different amounts and we get the hydrogen spectra on a screen. In the spectra of hydrogen atom, it is observed that light of wavelength 656.3 nm and then light of wave length 486.1 nm are present. Hydrogen atoms do not emit any radiation between 656.3 nm and 486.1 nm. Similarly radiation is observed at 434.1 nm and 4202.nm.
In the invisible region also, there is radiation emitted by the hydrogen atom at discrete wavelengths.
The wavelengths nicely fit the equation
1/λ = R [1/n² - 1/m²]
where R = 1.09737*10^7 m-1.
n and m are integers with m>n.
The spectrum in the ultraviolet region is called Lyman series and you get the series by setting n = 1.
The hydrogen spectrum in the visible region is called Balmer series and you get the series by setting n = 2.
The hydrogen spectrum in infrared region is called Paschen series and you get the series by setting n= 3.
Difficulties with Rutherford’s Model
Rutherford’s model assumes that the electron rotates around the nucleus. Maxwell’s equations of a electromagnetism show that accelerated electron must continuously emit electromagnetic radiation. But a hydrogen does not emit radiation at ground level energy or normal energy. It emits radiation only when heated. Also, if it emits radiation it will lose energy and the radius of its circular motion will decreases and finally it will fall into the nucleus. Hence, the atomic model proposed by Rutherford needs modification. Bohr proposed such modifications.
Bohr’s Model
Bohr’s postulates
1. The electrons revolve around the nucleus in circular orbits.
2. the orbit of the electron around the nucleus can be only some special values of radius. In these special radii orbits, the electron does not radiate energy as expected from Maxwell’s laws. These orbits are called stationary orbits.
3. The energy of the atom has a definite value when electrons are in a given stationary orbit. But the if more energy is provided to the atom, the electron can jump from one stationary orbit to another stationary orbit of higher energy. If it jumps from an orbit of higher energy (E2) to an orbit of lower energy (E1), it emits a photon of radiation. The energy of the emitted photon will be E2 – E1.
The wave length of the emitted radiation is given by the Einstein-Planck equation
E2-E1 = hυ = hc/λ
4. In stationary orbits, the angular momentum l of the electron about the nucleus is an in integral multiple of the Planck constant h divided by 2 π.
l = nh/2 π
This assumption is called Bohr’s quantization rule.
Energy of an Hydrogen Atom
Bohr’s postulated can be used to find the allowed energies of the hydrogen atom when its single electron is in various stationary orbits. The methodology can be used any hydrogen like ions which have only one electron.. Therefore it is valid for He+, Li++, Be+++ etc.
Assume that the nucleus has a positive charge Ze ( there are z protons each with positive charge e).
By equating the coulomb force acting between Ze and e to the centripetal acceleratin mv²/r, we get r the radius at which the electron revolves.
r = Ze²/4π ε0v²
From Bohr’s quantization rule,
mvr = nh/2 π
where n is a positive integer
Eliminating v from both the equations we get
r = ε0h²n²/πmZe²
We get expression for v as
v = Ze²/2 ε0hn
Hence allowed radii are proportinal to n² and for each value of n = 1,2,3…we allowed orbits.
The smallest radius orbit will have n = 1.
As we have expression for v, we can give an expression for kinetic energy when electron is in nth orbit is
K = ½ mv² = mZ²e4/8 ε0²h²n²
The potential energy of the atom is
V = - Ze²/4π ε0r = -mZ²e4/4ε0²h²n²
The expression for potential energy is obtained by assuming the potential energy to be zero when the nucleus and the electron are widely separated.
The total energy of the atom is
E = K+V = - mZ²e4/8 ε0²h²n²
When an atom is nth stationary orbit, it is said to be in the nth energy state.
In giving an expression for the total energy of the atom, kinetic energy of the electron and potential energy of theelectron-nucleus pair are considered. Kinetic energy of the nucleus is assumed to be negligible.
Radii or different orbits.
For hydrogen, z =1 and we get r1 as 53 picometre ( 1pm = 10^-12 m) or 0.053 nm. This length is called the Bohr radius and is a convenient unit for measuring lengths in atomic physics. It is denoted by me as the symbol a0 (In HC Verma a different symbol is given. I am using this symbol as a convenience).
In terms of Bohr radius the second allowed radius is 4 a0 and third is 9 a0 and so on. In general nth orbit of hydrogen atom is n²a0.
For a hydrogen like ion with Z protons in the nucleus,
rn = radius of ‘n’ th orbit = n²a0/Z
Energy at Ground and Excited states
From the total energy equation or expression we can find for hydrogen total energy when electron is in the state n = 1 (which is the ground state) as E1 = -13.6 eV. The radius corresponding to this energy is 53 picometre or 0.053 nm.
As in the energy equation only n changes with orbits, En is proportional to n².
There En = E1/n² = -13.6eV/n²
Note that the energy is expressed in negative units, so that larger magnitude means lower energy.
The state of an atom with the lowest energy is called its ground state.
The states with higher energies are called excited states.
Energy of hydrogen atom in the ground state is -13.6 eV.
Energy of hydrogen atom in the next excited state, that is n = 2 state is -3.4 eV.
Emission by Hydrogen Atom and Hydrogen spectra
When heated some atoms in the hydrogen become excited and when electrons jump from higher energy levels to lower energy levels in those excited atoms, photons with specific wavelengths are emitted or radiated.
If an electron jumps from mth orbit to nth orbit (m>n), the energy of the atom gets reduced from Em to En. The wavelength of the emitted radiation will be
1/ λ = (Em – En)/hc = RZ²{1/n² - 1/m²]
where R is the Rydberg constant.
R = 1.0973*10^7 m-
In terms of the Rydberg constant total energy of the atom in the nth state is E = -RhcZ²/n²
For hydrogen atom, when n =1, E = -Rhc and we know its value is -13.6 eV.
Energy of 1 rydberg means -13.6 eV.
Rhc = 13.6eV
Series structures
Lyman series:
All transitions to n =1 state from higher state give the radiation in Lyman series.
Jumping of the electron from n =2 to n =1 gives
1/ λ = R[1 – 1/2²] = R(1 – ¼) which will give λ = 121.6 nm.
Jumping of the electron from n = ∞ to n = 1 gives
1/ λ = R[1 – 1/∞²] = R(1 -0) which gives λ = 91.2 nm.
Balmer seires
All transitions to n = 2 from higher states given radiations within the range of 656.3 nm and 365.0 nm. These wavelengths fall in the visible region.
Paschen series
The transitions or jumps to n = 3 from higher energy levels give Paschen series in the range 1875 nm to 822 nm.
Ionization potential
The energy of the hydrogen atom in ground state is -13.6 eV. If we supply more than 13.6 eV to the hydrogen atom, the electron and the nucleus get separated and electron moves with some kinetic energy independently (Remember plasma in nuclear fusion).
The minimum energy needed to ionize an atom is called ionization energy. The potential difference through which an electron should be accelerated to acquire this much energy is called ionization potential.
Thus ionization energy of hydrogen atom in ground state is 13.6 eV and ionization potential is 13.6 V.
Binding energy
Binding energy of a system is defined as the energy released when its constituents are brought from infinity to form the system. Now we know that binding energy of a hydrogen atom is 13.6 eV. The energy is zero when the electron and nucleus at infinite distance. When the electron is brought into n = 1 orbit, the energy becomes -13.6 eV and hence 13.6 eV is released which is the binding energy.
Excitation potential
The energy needed to take the atom form its ground state to an excited state is called the excitation energy of that excited state.
As the hydrogen atom’s ground state energy is -13.6 eV and its energy when electron is in n =2 orbit is -3.4 eV, we have to supply 10.2 eV to excite a hydrogen atom to its first excited state which is electron in n = 2 orbit.
The potential through which an electron should be accelerated to acquire the excitation energy is the excitation potential.
The excitation potential needed bring hydrogen to its first excited state is 10.2 V.
Limitations of Bohr’s Model
Maxwell’s theory of electromagnetism is not replaced or refuted but it is arbitrarily assumed that in certain orbits, electrons get the licence to disobey the laws of electromagnetism and are allowed not to radiate energy.
The Wave Function of an Electron
Quantum mechanics describes the spectra in a much better way than Bohr’s model.
Electron has a wave character as well as a particle character. The wave function of the electron ψ(r,t ) is obtained by solving Schrodinger’s wave equation. The probability of finding an electron is high where | ψ(r,t )|² is greater. Not only the information about the electron’s position but information about all the properties including energy etc. that we calculated using the Bohr’s postulates are contained in the wave function of ψ(r,t).
Quantum Mechanics of the Hydrogen Atom
The wave function of the electron ψ(r,t) is obtained from the Schrodinger’s equation
-(h²/8π²m) [∂²ψ /∂x² + ∂²ψ /∂y² + ∂²ψ/∂z²] - Ze²ψ/4πε0r = E ψ
where
(x.y,z ) refers to a point with the nucleus as the origin and r is the distance of this point from the nucleus.
E refers to the energy.
Z is the number of protons.
There are infinite number of functions ψ(r,t) which satisfy the equations.
These functions may be characterized by three parameters n,l, and ml.
For each combination of n,l, and ml there is an associated unique value of E of the atom of the ion.
The energy of the wave function of characterized by n,l, and ml depends only on n and may be written as
En = - mZ²e4/8 ε0²h²n²
These energies are identical with Bohr’s model energies.
The paramer n is called the principal quantum number, l the orbital angular momentum quantum number and ml. The magnetic quantum number.
When n = 1, the wave function of the hydrogen atom is
ψ(r) = ψ100 = √(Z³/ π a0²) *(e-r/ a0)
ψ100 denotes that n =1, l = 0 and ml = 0
a0 = Bohr radius
In quantum mechanics, the idea of orbit is invalid. At any instant the wve function is spread over large distances in space, and wherever ψ≠ 0, the presence of electron may be felt.
The probability of finding the electron in a small volume dV is | ψ(r)| ² dV
We can calculate the probability p(r)dr of finding the electron at a distance between r and r+dr from the nucleus.
In the ground state for hydrogen atom it comes out to be
P(r) = (4/ a0)r²e -2r/ a0
The plot of P(r) versus r shows that P(r) is maximum at r = a0 Which the Bohr’s radius.
But when we put n =2, the maximum probability comes at two radii one near r = a0 and the other at r = 5.4 a0. According to Bohr model all electrons should be at r = 4 a0.
Nomenclature in Atomic Physics
An interesting property of electrons is that each electron has a spin angular momentum. It is characterized by ms and it can take values of +1/2 or -1/2.
Therefore a wave function is described by four characteristics n,l, ml and ms.
Any particular wave function described particular values of the above four characteristics or quantum numbers is termed a quantum state.
For n =1, l = 0 and ml = 0. Hence there will be two quantum states.
For n = 2 there 8 quantum states.
In general there are 2n² quantum states.
The quantum states corresponding to a particular n are together called a major shell.
n =1 shell is called K shell, n = 2 is called L shell and n = 3 shell is called M shell etc.
Pauli’s exclusion principle says that there cannot be more than one electron in any quantum state.
It is customary to use the symbols s,pd,f etc. to denote the value of the orbital angular momentum quantum number l corresponding to the value of l = 0,1,2,3 etc. respectively. These are called subshell for a given shell.
For an atom having many electrons, the quatum states are gradually filled from lower energy to higher energy to form the ground state of the atom.
Protons and neutrons also obey Pauli principle. They also have quantum numbers even though we do not study them in the current syllabus.
Any particle that obeys Pauli exclusion principle is called a fermion.
Electrons, protons, and neutrons are all fermions.
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Early Atomic Models
The idea that all matter is made of very small indivisible particles is very old.
Robert Boyle’s study of compression and expansion of air brings out the idea that air is made of tiny particles with lot of empty space between the particles.
The smallest unit of an element which carries all the properties of the element is called an atom.
Experiments on discharge tube, measurement of e/m by Thomson etc. established the existence of negatively charged electrons in the atoms.
Because atoms are electrically neutral, a search for the positive charge inside the atom was started.
Thomson’s Model of the atom
Thomson (1898) suggested that the atom is a positively charged solid sphere in which electrons are embedded in sufficient number to create a neutral atom. This model of the atom could explain why only negatively charged particles are being emitted when a metal is heated. This model was also useful to explain the formation of ions and ionic compounds.
Lenard’s Suggestion
Lenard observed that cathode rays are pssing through thin material without any deviation. According to him, this was so because, there is a lot of empty space in atoms. Hence the positive charged particles are also tiny like electrons.
Rutherford’s Model of the Atom
Rutherford experimented with alpha rays or particles. When he bombarded gold foils with alpha particles, Many went without deviation, some had some deviation and some were deflected by more than 90 and came back. Hence he made a conclusion that there was a particle with a mass equivalent to alpha particle inside the atom. The mass of an atom is concentrated in this particle.
The size of this particle was also estimated by Rutherford. Its linear size is 10 fermi ( 1 fermi is equal to 1 femtometre = 10^-15 m).
Rutherford proposed that the atom contains a positively charged tiny particle called nucleus. It contains the entire mass of the atom. Outside this nucleus, at some distance, electrons move around. The positive of charge of nucleus is exactly equal to the negative charge of the electrons of the atom.
Because electrons are very very light compared to the nucleus, due to heat only electrons come out.
Movement of electrons is to brought in and the coulomb force between the nucleus and the electron is assumed to provide only centripetal force to make the electron rotate in a circular motion.
Hydrogen Spectra
If hydrogen gas is enclosed in a sealed tube and heat to high temperatures, it emits radiation. If this radiation is passed through a prsim, components are different wavelengths get deviated by different amounts and we get the hydrogen spectra on a screen. In the spectra of hydrogen atom, it is observed that light of wavelength 656.3 nm and then light of wave length 486.1 nm are present. Hydrogen atoms do not emit any radiation between 656.3 nm and 486.1 nm. Similarly radiation is observed at 434.1 nm and 4202.nm.
In the invisible region also, there is radiation emitted by the hydrogen atom at discrete wavelengths.
The wavelengths nicely fit the equation
1/λ = R [1/n² - 1/m²]
where R = 1.09737*10^7 m-1.
n and m are integers with m>n.
The spectrum in the ultraviolet region is called Lyman series and you get the series by setting n = 1.
The hydrogen spectrum in the visible region is called Balmer series and you get the series by setting n = 2.
The hydrogen spectrum in infrared region is called Paschen series and you get the series by setting n= 3.
Difficulties with Rutherford’s Model
Rutherford’s model assumes that the electron rotates around the nucleus. Maxwell’s equations of a electromagnetism show that accelerated electron must continuously emit electromagnetic radiation. But a hydrogen does not emit radiation at ground level energy or normal energy. It emits radiation only when heated. Also, if it emits radiation it will lose energy and the radius of its circular motion will decreases and finally it will fall into the nucleus. Hence, the atomic model proposed by Rutherford needs modification. Bohr proposed such modifications.
Bohr’s Model
Bohr’s postulates
1. The electrons revolve around the nucleus in circular orbits.
2. the orbit of the electron around the nucleus can be only some special values of radius. In these special radii orbits, the electron does not radiate energy as expected from Maxwell’s laws. These orbits are called stationary orbits.
3. The energy of the atom has a definite value when electrons are in a given stationary orbit. But the if more energy is provided to the atom, the electron can jump from one stationary orbit to another stationary orbit of higher energy. If it jumps from an orbit of higher energy (E2) to an orbit of lower energy (E1), it emits a photon of radiation. The energy of the emitted photon will be E2 – E1.
The wave length of the emitted radiation is given by the Einstein-Planck equation
E2-E1 = hυ = hc/λ
4. In stationary orbits, the angular momentum l of the electron about the nucleus is an in integral multiple of the Planck constant h divided by 2 π.
l = nh/2 π
This assumption is called Bohr’s quantization rule.
Energy of an Hydrogen Atom
Bohr’s postulated can be used to find the allowed energies of the hydrogen atom when its single electron is in various stationary orbits. The methodology can be used any hydrogen like ions which have only one electron.. Therefore it is valid for He+, Li++, Be+++ etc.
Assume that the nucleus has a positive charge Ze ( there are z protons each with positive charge e).
By equating the coulomb force acting between Ze and e to the centripetal acceleratin mv²/r, we get r the radius at which the electron revolves.
r = Ze²/4π ε0v²
From Bohr’s quantization rule,
mvr = nh/2 π
where n is a positive integer
Eliminating v from both the equations we get
r = ε0h²n²/πmZe²
We get expression for v as
v = Ze²/2 ε0hn
Hence allowed radii are proportinal to n² and for each value of n = 1,2,3…we allowed orbits.
The smallest radius orbit will have n = 1.
As we have expression for v, we can give an expression for kinetic energy when electron is in nth orbit is
K = ½ mv² = mZ²e4/8 ε0²h²n²
The potential energy of the atom is
V = - Ze²/4π ε0r = -mZ²e4/4ε0²h²n²
The expression for potential energy is obtained by assuming the potential energy to be zero when the nucleus and the electron are widely separated.
The total energy of the atom is
E = K+V = - mZ²e4/8 ε0²h²n²
When an atom is nth stationary orbit, it is said to be in the nth energy state.
In giving an expression for the total energy of the atom, kinetic energy of the electron and potential energy of theelectron-nucleus pair are considered. Kinetic energy of the nucleus is assumed to be negligible.
Radii or different orbits.
For hydrogen, z =1 and we get r1 as 53 picometre ( 1pm = 10^-12 m) or 0.053 nm. This length is called the Bohr radius and is a convenient unit for measuring lengths in atomic physics. It is denoted by me as the symbol a0 (In HC Verma a different symbol is given. I am using this symbol as a convenience).
In terms of Bohr radius the second allowed radius is 4 a0 and third is 9 a0 and so on. In general nth orbit of hydrogen atom is n²a0.
For a hydrogen like ion with Z protons in the nucleus,
rn = radius of ‘n’ th orbit = n²a0/Z
Energy at Ground and Excited states
From the total energy equation or expression we can find for hydrogen total energy when electron is in the state n = 1 (which is the ground state) as E1 = -13.6 eV. The radius corresponding to this energy is 53 picometre or 0.053 nm.
As in the energy equation only n changes with orbits, En is proportional to n².
There En = E1/n² = -13.6eV/n²
Note that the energy is expressed in negative units, so that larger magnitude means lower energy.
The state of an atom with the lowest energy is called its ground state.
The states with higher energies are called excited states.
Energy of hydrogen atom in the ground state is -13.6 eV.
Energy of hydrogen atom in the next excited state, that is n = 2 state is -3.4 eV.
Emission by Hydrogen Atom and Hydrogen spectra
When heated some atoms in the hydrogen become excited and when electrons jump from higher energy levels to lower energy levels in those excited atoms, photons with specific wavelengths are emitted or radiated.
If an electron jumps from mth orbit to nth orbit (m>n), the energy of the atom gets reduced from Em to En. The wavelength of the emitted radiation will be
1/ λ = (Em – En)/hc = RZ²{1/n² - 1/m²]
where R is the Rydberg constant.
R = 1.0973*10^7 m-
In terms of the Rydberg constant total energy of the atom in the nth state is E = -RhcZ²/n²
For hydrogen atom, when n =1, E = -Rhc and we know its value is -13.6 eV.
Energy of 1 rydberg means -13.6 eV.
Rhc = 13.6eV
Series structures
Lyman series:
All transitions to n =1 state from higher state give the radiation in Lyman series.
Jumping of the electron from n =2 to n =1 gives
1/ λ = R[1 – 1/2²] = R(1 – ¼) which will give λ = 121.6 nm.
Jumping of the electron from n = ∞ to n = 1 gives
1/ λ = R[1 – 1/∞²] = R(1 -0) which gives λ = 91.2 nm.
Balmer seires
All transitions to n = 2 from higher states given radiations within the range of 656.3 nm and 365.0 nm. These wavelengths fall in the visible region.
Paschen series
The transitions or jumps to n = 3 from higher energy levels give Paschen series in the range 1875 nm to 822 nm.
Ionization potential
The energy of the hydrogen atom in ground state is -13.6 eV. If we supply more than 13.6 eV to the hydrogen atom, the electron and the nucleus get separated and electron moves with some kinetic energy independently (Remember plasma in nuclear fusion).
The minimum energy needed to ionize an atom is called ionization energy. The potential difference through which an electron should be accelerated to acquire this much energy is called ionization potential.
Thus ionization energy of hydrogen atom in ground state is 13.6 eV and ionization potential is 13.6 V.
Binding energy
Binding energy of a system is defined as the energy released when its constituents are brought from infinity to form the system. Now we know that binding energy of a hydrogen atom is 13.6 eV. The energy is zero when the electron and nucleus at infinite distance. When the electron is brought into n = 1 orbit, the energy becomes -13.6 eV and hence 13.6 eV is released which is the binding energy.
Excitation potential
The energy needed to take the atom form its ground state to an excited state is called the excitation energy of that excited state.
As the hydrogen atom’s ground state energy is -13.6 eV and its energy when electron is in n =2 orbit is -3.4 eV, we have to supply 10.2 eV to excite a hydrogen atom to its first excited state which is electron in n = 2 orbit.
The potential through which an electron should be accelerated to acquire the excitation energy is the excitation potential.
The excitation potential needed bring hydrogen to its first excited state is 10.2 V.
Limitations of Bohr’s Model
Maxwell’s theory of electromagnetism is not replaced or refuted but it is arbitrarily assumed that in certain orbits, electrons get the licence to disobey the laws of electromagnetism and are allowed not to radiate energy.
The Wave Function of an Electron
Quantum mechanics describes the spectra in a much better way than Bohr’s model.
Electron has a wave character as well as a particle character. The wave function of the electron ψ(r,t ) is obtained by solving Schrodinger’s wave equation. The probability of finding an electron is high where | ψ(r,t )|² is greater. Not only the information about the electron’s position but information about all the properties including energy etc. that we calculated using the Bohr’s postulates are contained in the wave function of ψ(r,t).
Quantum Mechanics of the Hydrogen Atom
The wave function of the electron ψ(r,t) is obtained from the Schrodinger’s equation
-(h²/8π²m) [∂²ψ /∂x² + ∂²ψ /∂y² + ∂²ψ/∂z²] - Ze²ψ/4πε0r = E ψ
where
(x.y,z ) refers to a point with the nucleus as the origin and r is the distance of this point from the nucleus.
E refers to the energy.
Z is the number of protons.
There are infinite number of functions ψ(r,t) which satisfy the equations.
These functions may be characterized by three parameters n,l, and ml.
For each combination of n,l, and ml there is an associated unique value of E of the atom of the ion.
The energy of the wave function of characterized by n,l, and ml depends only on n and may be written as
En = - mZ²e4/8 ε0²h²n²
These energies are identical with Bohr’s model energies.
The paramer n is called the principal quantum number, l the orbital angular momentum quantum number and ml. The magnetic quantum number.
When n = 1, the wave function of the hydrogen atom is
ψ(r) = ψ100 = √(Z³/ π a0²) *(e-r/ a0)
ψ100 denotes that n =1, l = 0 and ml = 0
a0 = Bohr radius
In quantum mechanics, the idea of orbit is invalid. At any instant the wve function is spread over large distances in space, and wherever ψ≠ 0, the presence of electron may be felt.
The probability of finding the electron in a small volume dV is | ψ(r)| ² dV
We can calculate the probability p(r)dr of finding the electron at a distance between r and r+dr from the nucleus.
In the ground state for hydrogen atom it comes out to be
P(r) = (4/ a0)r²e -2r/ a0
The plot of P(r) versus r shows that P(r) is maximum at r = a0 Which the Bohr’s radius.
But when we put n =2, the maximum probability comes at two radii one near r = a0 and the other at r = 5.4 a0. According to Bohr model all electrons should be at r = 4 a0.
Nomenclature in Atomic Physics
An interesting property of electrons is that each electron has a spin angular momentum. It is characterized by ms and it can take values of +1/2 or -1/2.
Therefore a wave function is described by four characteristics n,l, ml and ms.
Any particular wave function described particular values of the above four characteristics or quantum numbers is termed a quantum state.
For n =1, l = 0 and ml = 0. Hence there will be two quantum states.
For n = 2 there 8 quantum states.
In general there are 2n² quantum states.
The quantum states corresponding to a particular n are together called a major shell.
n =1 shell is called K shell, n = 2 is called L shell and n = 3 shell is called M shell etc.
Pauli’s exclusion principle says that there cannot be more than one electron in any quantum state.
It is customary to use the symbols s,pd,f etc. to denote the value of the orbital angular momentum quantum number l corresponding to the value of l = 0,1,2,3 etc. respectively. These are called subshell for a given shell.
For an atom having many electrons, the quatum states are gradually filled from lower energy to higher energy to form the ground state of the atom.
Protons and neutrons also obey Pauli principle. They also have quantum numbers even though we do not study them in the current syllabus.
Any particle that obeys Pauli exclusion principle is called a fermion.
Electrons, protons, and neutrons are all fermions.
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Friday, October 3, 2008
IIT JEE Material Updated
Material relating to chapters x-rays and Nucleus updated.
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