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Section 1 Atomic Structure

Cambridge A-level Chemistry Centre of Pre-U Studies

Overview of Section 2
Content:

Describe the atom in terms of protons and neutrons in the nucleus Explain and describe the electrons in terms of energy levels, ionisation energy, atomic orbitals and extranuclear structure

Defining the Atom

The Greek philosopher Democritus (460 B.C. 370 B.C.) was among the first to suggest the existence of atoms (from the Greek word atomos)
He

believed that atoms were indivisible and indestructible His ideas did agree with later scientific theory, but did not explain chemical behavior, and was not based on the scientific method but just philosophy

Viewing Surface of metal using STM

Blue platinum Blue Nickel

Daltons Atomic Theory (experiment based)


1) All elements are composed of tiny indivisible particles called atoms 2) Atoms of the same element are identical. Atoms of any one element are different from those of any other element.

John Dalton (1766 1844)

3) Atoms of different elements combine in simple whole-number ratios to form chemical compounds 4) In chemical reactions, atoms are combined, separated, or rearranged but never changed into atoms of another element.

Section 2 Structure of the Nuclear Atom


Review:
Discovery

of subatomic

particles.

Thomsons Atomic Model

J. J. Thomson

Thomson believed that the electrons were like plums embedded in a positively charged pudding, thus it was called the plum pudding model.

Ernest Rutherfords Gold Foil Experiment - 1911

Alpha particles are helium nuclei The alpha particles were fired at a thin sheet of gold foil Particle that hit on the detecting screen (film) are recorded

Rutherfords Findings
Most of the particles passed right through A few particles were deflected VERY FEW were greatly deflected

Like howitzer shells bouncing off of tissue paper!

Conclusions:
a) The nucleus is small b) The nucleus is dense c) The nucleus is positively

charged

The Rutherford Atomic Model

Based on his experimental evidence: The atom is mostly empty space All the positive charge, and almost all the mass is concentrated in a small area in the center. He called this a nucleus The nucleus is composed of protons and neutrons The electrons distributed around the nucleus, and occupy most of the volume His model was called a nuclear model

Section 2 Structure of the Nuclear Atom


One

change to Daltons atomic theory is that atoms are divisible into subatomic particles:
Electrons,

protons, and neutrons are examples of these fundamental particles There are many other types of particles, but we will study these three

Discovery of the Electron


In 1897, J.J. Thomson used a cathode ray tube to deduce the presence of a negatively charged particle: the electron

Question May 2002


Sir James Jean who was a great populariser of science, once described an atom of carbon as being like six bees buzzing around a space the size of a football stadium. (a)(i) suggest what were represented by the six bees in this description. (ii) explain(in terms of an atom of carbon) what stopped the bees from flying away from the space of the football stadium. (iii) what is missing from Jeans description when applied to an atom of carbon?

Atomic particles Section 2(a),(b),(c) Identify and describe protons,neutrons and electrons in terms of their relative charges and relative masses. Deduce the behavior of beams of protons, neutrons and electrons in electric fields. Describe the distribution of mass and charges within an atom

Mass of the Electron


Mass of the electron is 9.11 x 10-28 g

The oil drop apparatus

1916 Robert Millikan determines the mass of the electron: 1/1840 the mass of a hydrogen atom; has one unit of negative charge

Conclusions from the Study of the Electron:


a) Cathode rays have identical properties regardless of the element used to produce them. All elements must contain identically charged electrons. b) Atoms are neutral, so there must be positive particles in the atom to balance the negative charge of the electrons c) Electrons have so little mass that atoms must contain other particles that account for most of the mass

Conclusions from the Study of the Electron:


Eugen Goldstein in 1886 observed what is now called the proton particles with a positive charge, and a relative mass of 1 (or 1840 times that of an electron) 1932 James Chadwick confirmed the existence of the neutron a particle with no charge, but a mass nearly equal to a proton

Summary Table
Therefore Modern picture of an atom, then, consist of three types of particles-electrons, protons and neutron.
Electric Charge Particle SI (C ) Atomic Electron -1.602x10-19 -1 Proton +1.602x10-19 +1 Neutron 0 0 Mass SI (g) 9.109x10-28 1.673x10-24 1.675x10-24

amu 5.49x10-4 1.0073 1.0087

Located outside nucleus in nucleus in nucleus

Subatomic Particles
Particle
Electron (e-) Proton (p+)

Rel Charge
-1

Rel Mass

Location

1/1840

Electron cloud

+1 0

1 1

Nucleus Nucleus

Neutron (no)

Deflection of atomic particles


Interaction of charged particles in electric field Non-interaction of Non-charged particles in electric field Direction of deflection depends on the charge of the particle Magnitude of deflection depends on the mass of the atomic particles when the magnitude of charge is the same

Question 1.Beams of particles traveling at the same speed from different sources are subjected to an electric field as shown in the diagram below. A beam of neutrons has already been drawn.

Sketch on the diagram above how beams of each of the following particles are affected by the electric field: (i) protons; (ii) electrons; (iii)
2 1H

Label each of the beams. Explain briefly the position and shape of each beam: (i) protons;(ii) electrons and (iii) 21H

Section 2(d)

Learning Outcomes

Deduce the numbers of protons, neutrons and electrons present in both atoms and ions given proton and nucleon numbers( and charge)

Proton Number
Atoms are composed of protons, neutrons, and electrons How then are atoms of one element different from another element? Elements are different because they contain different numbers of PROTONS The proton number of an element is the number of protons(#) in the nucleus

protons in an atom = # electrons

Proton Number
Proton number (Z) of an element is the number of protons in the nucleus of each atom of that element.
Element
Carbon

# of protons
6

Z
6

Phosphorus
Gold

15
79

15
79

Nucleon Number(A)
Nucleon number is the number of protons and neutrons in the nucleus of an isotope: A = p+ + n0 Nuclide
Oxygen - 18
Arsenic - 75 Phosphorus - 31

p+
8 33
15

n0
10 42
16

e8
33
15

A
18 75 31

Complete Symbols
Contain the symbol of the element, the nucleon number and the proton number. Nucleon Superscript Number(A)

Subscript

Proton Number(Z)

Symbols

Find each of these: a) number of protons b) number of neutrons c) number of electrons d) Proton number e) Nucleon Number

80 35

Br

Symbols

If an element has an proton number of 34 and a nucleon number of 78, what is the: a) number of protons b) number of neutrons c) number of electrons d) complete symbol

Symbols If an element has 91 protons and 140 neutrons what is the a) Proton number b) Nucleon number c) number of electrons d) complete symbol

Symbols If an element has 78 electrons and 117 neutrons what is the a) Proton number b) Nucleon number c) number of protons d) complete symbol

Note

In a neutral atom , the number of electrons is equal to the number of protons. In a negative ion (anion), the number of electrons is greater than the number of protons since a negative ion is obtained by adding electron(s) to a neutral atom. In a positive ion(cation), the number of electrons is less than the number of protons since a positive ion is obtained by removing electron(s) from a neutral atom.

Ions

is an electrically charged particle obtained from an atom or chemically bonded group of atoms lose or gain electrons. The charge on an ion is equal to the # of protons minus the # of electrons. An atom that gains extra electrons becomes a negatively charged ion, called an anion. An atom that loses electrons becomes positively charged ion, called a cation. number p + number n number p - number e A +?

number p

E Z

E.g. Determine numbers of electrons in Mg2+ cation and the S2anion? Mg2+ 12-number e = +2 S216-number e = -2 number e =10 number e =18

32 15

32 15

P 3

May/June 2008

32 15

Skin cancer can be treated using a radioactive isotope of phosphorus,3215P . A compound containing the phosphide ion 3215P3- , is wrapped in a plastic sheet, is strapped to the affected area. What is the composition of the phosphide ion, 3215P3 ?

Protons A B C D 15 15 17 32

Neutrons 17 17 15 17

electrons 18 32 17 15

Section 2.3(e)(II) Distinguishing Among Atoms


Learning

Outcome:

Distinguish

between isotopes on the basis of different numbers of neutrons present

Isotopes
Dalton was wrong about all elements of the same type being identical Atoms of the same element can have different numbers of neutrons.( see next slide) Thus, different nucleon numbers. These are called isotopes. Isotopes have the same chemical properties but different properties(e.g denstiy, mass)

Isotopes
Elements occur in nature as mixtures of isotopes.

Naming Isotopes
We

can also put the nucleon number after the name of the element:
carbon-12 carbon-14 uranium-235

Isotopes are atoms of the same element having different masses, due to varying numbers of neutrons.
Isotope Protons Electrons Neutrons Nucleus

Hydrogen1 (protium) Hydrogen-2 (deuterium) Hydrogen-3 (tritium)

1 1 1

1 1 1

0 1 2

i)

Define the term isotopes.

[2] ii) Br has 2 main isotopes. Complete the table below show the atomic structure of these isotopes. [2]
-

Isotope
79Br
81Br

Protons

Neutrons

Electrons

iii)

The percentage composition by mass of the isotopes in part (b) is 50.5% 79Br and 49.5% 81Br. Use this data to calculate the relative atomic mass of bromine to three significant figures.

[2]

Other types of particles

Our understanding of atom is still in growing. The unknowns are yet to be discovered.

Question May/June 2007


John Daltons atomic theory, published in 1808, contained four predictions about atoms. Which of his predictions is still considered to be correct A Atoms are very small in size B No atom can be split into simpler parts C All the atoms of a particular element have the same mass D All the atoms of one element are different in mass from all the atoms of the other elements

Question31 May/June 2007


Use of the Data Booklet is relevant to this question. The technetium-99 isotope( 99Tc) is radioactive and has been found in lobsters and seaweed adjacent to nuclear fuel reprocessing plants Which statements are correct about an atom of 99Tc? 1. It has 13 more neutrons than protons. 2. It has 43 protons. 3. It has 99 nucleons.

Orbitals Section 2(f)


Learning

Outcomes

Describe

the number and relative energies of the s,p, and d orbitals for the principal quantum numbers 1, 2, and 3 and also the 4s and 4p Describe the shapes of s and p orbitals

What is an orbital?

An atomic orbital is a region of space(3 dimensional) round the nucleus in which the probability of finding a particular electron( in a free atom) is the greatest. Electrons can occupy four types of orbital, which differ from each other in shape and in their orientation in space. These are called s,p, d and f orbitals.

s orbitals are spherical p orbitals are dumb-bell-shaped and can be arranged in different directions.

Shapes of the orbitals

s,p and d- orbitals

Question
Sketch the shapes of and spatial distributions of all the occupied orbitals in nitrogen

Answers

1s

2s

2pz

2px

2py

Modern Atomic Theory


The Principal Quantum Number (n) Represents the energy level of highest probability.
n=1 n=2 n=3

Analogy

A ladder A bookshelf View video on atom

What is a shell?

A shell is a group of orbitals that are about the same distance out from the nucleus.
Shells are numbered starting with the shell nearest to the nucleus and working outwards Each successive shell has a different number of orbitals in it. In the nth shell, there are n sub-shells, n2 orbitals and a maximum of 2n2 electrons.

No. of shells and No. of electrons


shell No. of s p d f Max. no. of electrons orbitals(n2) in shell( 2n2) n=1 1 1 2 n=2 4 n=3 9 n-=4 16 1 3 1 35 8 18

1 3 5 7 32

What is a sub-shell?

A sub-shell is a group of orbitals with the same energy level, but differ in their orientation in space, e.g. the second shell (n=2) contains two sub-shells:
a sub-shell containing one s orbital, and a sub-shell containing three p orbitals: 2px,2py,2pz

Section 2(h)

Learning Outcome

State the electronic configuration of atoms and ions given the proton number( and charge)

What is meant by electronic configurations?

The electronic configuration of an element describes how the element of its atoms are arranged in their shells, sub-shells and orbitals.

Filling of orbitals

In an atom, the orbitals are filled in order of increasing energy(starting from 1s) according to the following rules.

Electronic Energy Level


An Energy Diagram
Rules for assigning electrons 1. Occupy lowest levels first.(Aufbau Principle) 2. 3d ___ ___ ___ ___ ___ Allowed 2 electrons in each orbital. If 2, must 3p ___ ___ ___ have opposite spins. [Pauli Exclusion Principle] 3s ___ 3. Fill sub-level before 2p ___ ___ ___ moving up.(Hunds Rule of Multiplicity) 2s ___ n=1 1s 4. 1 electron in each orbital of the same energy(degenerate) before doubling up. To keep electron spins the same before thay are occupied in pair)

N=3

n=2

Electronic Configurations
The Electron Configuration A short hand method for notating the electronic structure of atoms. Write the electron configuration for sodium. Sodium has 11 electrons. We know this because it has an atomic number of 11 which means it has 11 protons and thus must have 11 electrons. 1s22s2p63s1 or [Ne]3s1

Modern Atomic Theory


An Energy Diagram
3d ___ ___ ___ ___ ___ n=3 3p ___ ___ ___ 3s ___ 2p ___ ___ ___ n=2 2s ___ n=1 1s

1s22s22p63s1

Question Oct 2001


Give the full electron configuration of the following (i) Mg (ii) Mg 2+ (iii) O (iv) O 2-

Question
Construct a schematic diagram representing the number and relative energies of the orbitals of the first three principal quantum numbers.

Answers
3d

3p
3s Energy 2p 2s

1s

Question
Show the electronic configuration of nitrogen using the diagram in the previous answer

Answer

Energy

2p 2s

1s

Isoelectronic

Atoms that have the same number of electrons are known as isoelectronic.

Oct/Nov 2007
Use the Data Booklet is relevant to this question. In forming ionic compounds, elements generally form an ion with the electronic structure of a noble gas. Which ion does not have a noble gas electronic structure?
A. IB Rb+ C Sn 2+ D Sr 2+

Representing electronic configuration

By using electrons-in-boxes Using a noble gas core Using the s, p, d and f notation

Using energy levels

Ionisation Energy Sect.2(j)

Learning Outcomes
(i) explain and use of the term ionisation energy (ii) explain the factors influencing the ionisation energies of elements (iii) explain the trends in ionisation energies across a period and down a group of the Periodic Table.

Definition of IE

The energy to remove an electron from each atom/ion in a mole of atoms/ions of an element in the gaseous state Refer to data booklet for successive IE energies

Consecutive IE of a single element or atom

Generally increase of IE is due to the consecutive electron removed because it is harder to remove electrons from the more positive ion. Large rise of IE implies that electron are removed from a different principal shell. Small increase of IE represent change in subshell.

Explanation of IE

Explain large rise in IE. When all valence shell electrons are removed, only the inner shell remains. The inner shell experience much less shielding , resulting in a higher nuclear attraction and therefore lead to a much higher IE big jump Explain small increase in IE. Electrons in higher level subshell removed first; after which electrons from lower energy subshell removed. For example, 3p electrons are removed before 3s. Lower subshell electron experience slightly higher nuclear attraction and therefore slightly higher IE small jump

Factors influencing IE

The size of the positive nuclear charge The distance of the electron from the nucleus The shielding effect by electrons in filled inner shells

Explaining the IE trends

Increase across the period

Across the period, nuclear attraction on the valence electron increases. This is due to the increase in proton number,Z but a fairly constant shielding
Down the group, nuclear attraction on the valence electron decreases. This is due to great increase in Screening Effect,SE with atom having more inner shells.

Decrease down the group

IE trend ACROSS period


IE depends on the effect of the nuclear attraction on the valence electron. Across the period, IE increases since the proton number increases but the shielding effect remains fairly constant. IE do not increase uniformly. Small kink may be produced, where the IE is lower than normal. 2 possible reasons(i) electron is removed from the higher energy subshell. Less energy is required to remove p-electron (ii) paired vs unpaired electron is removed. Paired electron experiences repulsion makes a removal easier( use only in p orbital) Always write out the electronic configuration to figure out the reason for non-uniformity.

IE down the group

IE down the group will decrease dramatically, since the effect of the nuclear attraction on the valence electron decreases significantly due to increase in number of principal quantum electron shells(inner shells) . Outer shell experiences much higher shielding effect which outweighs(greater weight attached to the effect) increase of nuclear charge. SE > Z

Importance of IE

To predict or confirm the simple electronic configurations of elements An example. the first four IE of an element are, in kJ per mol: 590,1150,4940,6480. Suggest the Group in the Periodic table to which this element belongs

Oct/Nov 2007

The graph show the first thirteen IE ionisation energies for element X What can be deduced about element X from the graph? A It is in the second period (Li-Ne) of the Periodic Table B It is a d-block element C It is in the Group II of the Periodic Table D It is in Group III of the Periodic Table

i)

Define the term first ionisation energy and write an equation to represent the first ionisation energy of chlorine. Definition

[3] Equation ii) Write an equation to show the fourth ionisation energy of nitrogen. Equation iii) State and explain the trend in first ionisation energies down group 2 in the Periodic Table. [2]

[2]

[4]

The successive ionisation energies for nitrogen are show below.

Ionisation number
i)

1st

2nd

3rd

4th

5th

6th

7th

Ionisation energy / kJmol1 1402 2856 4578 7475 9445 53268 64362
Explain why the successive ionisation energies show a general increase.

[2]

ii)

What can be deduced about the electronic structure of the nitrogen atom? Explain your deductions carefully.

[4]

i) ii) iii)

Define the term isotope. Br has 2 main isotopes. Complete the table below show the atomic structure of these isotopes. The percentage composition by mass of the isotopes in part (b) is 50.5% 79Br and 49.5% 81Br. Use this data to calculate the relative atomic mass of bromine to three significant figures.

Mark scheme i) Substances consisting of atoms with same atomic number / same number of protons / of the same element 1 but with different mass number / different numbers of nucleons / different neutron numbers 1 ii)

Isotope
iii)

Protons

Neutrons

Electrons
35 35
1

79 all 2 marks Br correct 35 1 mark 1 row or 2 columns correct 79 35 = 44 A r =81 x 0.505) + (81 x 0.495) (79 Br 35 81 35 = 46 = 79.99% 80.0% to 3 sig. figs.

i)

ii) iii)

Define the term first ionisation energy and write an equation to represent the first ionisation energy of chlorine. [5] Write an equation to show the fourth ionisation energy of nitrogen. [2] State and explain the trend in first ionisation energies down group 2 in the Periodic Table. [3]

Mark scheme i) Definition:

ii) iii)

Energy required to remove first electron from each atom 1 in one mole of 1 gaseous atoms (to form one mole of gaseous +1 ions) 1 Equation: Cl (g) Cl + (g) + e 1 for species, 1 for state symbols N +3 (g) +4 (g) + e 1 for species, 1 for state symbols First ionisation energies decrease as group 2 is descended 1 Number of shells and hence atomic radii increase down the group 1 Greater number of shells means shielding increases 1 Overall, the outer shell electrons are further from the nucleus and less strongly attracted to it 1 These factors are more important than the increase in nuclear charge 1 Maximum 4 marks

The successive ionisation energies for nitrogen are show below. Ionisation number 1st 2nd 3rd 4th 5th 6th 7th i) Explain why the successive ionisation energies show a general increase. [2] Ionisation energy / kJmol1 1402 2856 4578 7475 9445 53268 64362 ii) What can be deduced about the electronic structure of the nitrogen atom? Explain your deductions carefully. [4]

Mark scheme i) Negative electrons are being removed from an increasingly positive ion / there is a greater proton to electron ratio. 1 The attraction between the nucleus and the remaining electrons increases. 1 Also, the repulsion amongst the remaining electrons decreased 1 Maximum 2 marks ii) There is a large increase in ionisation energy when the 6th electron is removed. 1 The 6th electron is removed from a new shell 1 that is closer to the nucleus with less shielding. 1 Within a shell, the increase in ionisation energy is much smaller. 1 So nitrogen has 5 electrons in outer shell and 2 in shell closer to the nucleus. 1 Maximum 4 marks