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An atomic emission spectrum can be obtained by passing the light emitted from the
discharge tube through a prism. Light consists of a wide range of radiation of different
frequencies is spilt by the prism.
Coloured lines are seen on the dark background.
The hydrogen emission spectrum is seen to be a number of series of lines. These groups of
lines were named after scientists who discovered them.
where h is the Planck constant (普 朗 克 常 數 ) (h = 6.63 × 10-34 Js) and c is the speed of light
(c = 3 × 108 ms-1)
For an electron to move from an orbit of energy E1 to another orbit with energy E2, the light
absorbed must have a frequency give by Planck’s Equation (i.e. v is fixed):
When electrons which have been excited (raised to orbits of higher energy) drop back to
orbits of lower energy, they emit energy as light with a frequency given by Planck’s equation
(again, v is fixed)
n=∞ E∞
n=4 E4
n=3 E3
n=2 E2
E2 (excited state)
E1 (ground state)
When an electron falls from a higher energy level to a lower energy level, it emits a quantum
of energy (ΔE) in radiation of definite frequency. Since ΔE for the change is always the
same in a given atom, ν must be a constant.
Therefore, radiation always has the same energy and is always of the same frequency for that
particular electron transition.
Hence, the atomic emission spectrum consists of discrete lines.
For example, transitions from n = 3 to n = 2 result in the first line of the series which is
a red line (at frequency 4.571 × 1014 Hz) in the hydrogen spectrum, while transitions
from n = 4 to n = 2 produce the second line (a blue line at frequency 6.172 × 1014 Hz).
(Question: Calculate the energy difference between energy levels of n = 3 and n = 2.)
At higher energies, the energy levels get closer and eventually come together, it follows
that the spectral lines also get closer and eventually come together. This particular
frequency is called the convergence limit.
Hint: When working on calculations about ionization energy, you should be very
careful about whether you need to calculate the I.E of “one hydrogen atom” or “one
mole of hydrogen atom”. (For the latter case, you have to multiply the value by the
Avogadro constant)
Energy is always absorbed in this process because work has to be done in overcoming the
attractive force of the positively charged nucleus for the negatively charged electrons. (電離
焓必定是正值,是吸熱反應。因為要克服原子核和電子之間的吸引力)
The first ionization energy is the minimum energy required to remove the most loosely held
electron.
That is, the electron in the outermost shell (∵smallest attraction from the nucleus).
More specifically, the 1st I.E. is the energy required to remove an electron from a
free atom in gaseous state.
X(g) → X+(g) + e– ∆ H = 1st I.E.
The energy needed to remove the next electron is the second ionization enthalpy, and so on.
When an electron is removed, the atom has a net positive charge so that the next electron is
more difficult to remove because of large attraction between positive ion and negatively
charged electron.
i.e. first ionization energy < second ionization energy and in general:
1st I.E. < 2nd I.E. < 3rd I.E.
Take potassium as an example, the ionization of potassium can take place in steps
1st ionization
K(g) → K+(g) + e–
ΔHI1 = 419 kJmol–1
2nd ionization
K+(g) → K2+(g) + e–
ΔHI2 = 3051 kJmol–1
3rd ionization
K2+(g) → K3+(g) + e–
ΔHI3 = 4412 kJmol–1
Consider the plot of log ionization enthalpy against the number successive ionization
enthalpy of potassium atom:
There is a general increase in successive ionization with the no. of electrons removed. It
is due to the nucleus becoming more positively-charged as each electron is being lost.
The electrostatic attraction between the ion and electron increases as the charge of
cation increases. So more energy is needed to remove the electron.
The 1st I.E. of sodium is much less than the 2nd I.E. This is due to the 1st electron is removed
The 1st I.E. increases roughly across a period due to the increase in nuclear charge.
Besides the main trends, some irregularities are found within a period. For instance, in
period 2 and 3, the increasing trends can further be broken up into 3 parts, in a 2-3-3
manner.
This suggests the presence of sub-shells (s, p, d and f sub-shells) within an electron
shell (n = 1, 2, 3 ...)
Those sub-shells may have small difference in energy which makes the 1st I.E. of some
elements in the same shell different.
Conclusion: The pattern of 1st I.E. of various elements indicates that there are
further subdivisions of energy within some shells called sub-shells.
When we consider the 1st I.E. down a group, the trend will be as follows:
Going down a group, the 1st I.E. decreases as the number of electron shells or the size
of the atom increases.
The attraction between the outermost electron and the nucleus decreases with
increasing atomic size.
A prevailing explanation for these variations in ionization energy is that there are
subdivisions of energy within some sub-shells, which are called orbitals (軌 態 ). Different
electrons occupy different orbitals in an atom.
Take the third energy level (n = 3) as an example:
It is suggested that different orbitals have different energies, the electron in different
orbital shows difference in energy. A more energetic electron would be removed more
readily and has lower ionization energy.
The details about the atomic orbitals will be discussed in the following part.
Following this, studies in quantum mechanics have shown that electrons are not localized in
fixed orbits, and as a matter of fact, we can find only describe the location of an electron in
terms of probability of finding it in a certain position at any time.
The probability, considered over a period of time, gives an average picture of how the
electron behaves. The picture does not show the actual location of the electron at any given
time. Instead, it shows where the electron is most likely to be at any time.
To sum up, the electrons are moving in all directions within the atom, forming an electron
cloud (電子雲).
電 子在原子核外很小的空間內作高速運動,其運動規律跟一般物體不同,它
沒有明確的軌道。根據量子力學中的不確定性原理 (Uncertainty principle),我
們 不 可 能同 時準 確地 測定 出電 子在 某一 時刻 所處 的位 置和 動量 (運動 速度 ),
也 不能描畫出它的運動軌跡。因此,人們常用一種能夠表示電子在一定時間
內 在核外空間各處出現機會的模型來描述電子在核外的運動。在這個模型裡 ,
The following figure shows the probability distribution of the electron in a hydrogen atom:
The denser the dots, the more likely the electron will be in that region. However, even at
points far away from the nucleus there is some probability, although it is small.
More specifically the volume of the space in which there is a high probability (≧ 90%) of
finding the electron is called the atomic orbital.
An atomic orbital can be viewed as a representation of a region within which there is a very
high probability of finding an electron.
It can also be regarded as the space in an atom occupied by an electron, a subdivision of
the available space within an atom for an electron to orbit the nucleus.
This new atomic model is called wave-mechanical model (波動模型) and it was developed
by Erwin Schrödinger, an Austrian physicist in 1926.
In this model, electrons are considered as both particles and waves:
Not localized in fixed orbits
Their arrangements and motions are described by mathematical equations
We describe an electron in terms of the probability of finding it
*Notes:
1. If a magnetic field is supplied, the subshell is shown to consist of “sub-subshells”, each
having a quantized spatial orientation in a magnetic field.
2. Electrons with different subsidiary quantum numbers can be denoted by the letters s, p, d
and f, or s orbital, p orbital, d orbital and f orbital.
Value of l 0 1 2 3
Orbital s p d f
3. Each orbital only maximum holds 2 electrons. Both of them have opposite spin (will be
discussed later).
The relative energies of different orbitals increase as the principal quantum number
increases.
For a one-electron system like hydrogen atom, the division will be as follows:
The situation for many-electron systems will be more complex. The energies of subshells
increase in the order s < p < d < f. The relative energy level diagram of orbitals is shown in
the following figure:
The p orbitals are all dumb-bell in shape (啞 鈴形 ). They are directional and lie along
any of the three coordinate axes (The figure below shows the three 2p orbitals).
Having the knowledge on atomic orbitals, we can go further to build up a new concept on
electronic configuration of atoms.
This is because extra stability can be gained by have some special configurations – half-
filled (e.g. np3, nd5) or completely/full-filled subshells (e.g. ns2, np6, nd10) (半滿或者全滿
的電子亞層能夠賦予原子額外的穩定性。).
Half-filled subshells attain extra stability because electrons in those subshells are
evenly distributed in different orbitals and have parallel spin. As a result, the
electronic repulsion can be reduced.
Completely filled subshells attain even higher stability because extra energy is
required to break the arrangement of paired electrons with different spins (spin
paired arrangement). One common example is ns2np6, which is known as the stable
noble gas electronic configuration.
The concept of “extra stability” can also be used to explain the irregularities in the variation
of 1st I.E. across a period.’
For example, the 1st I.E. of oxygen is lower than that of nitrogen because nitrogen
atom has a half-filled 2p subshell which gives it extra stability (∴more difficult to
remove electron).
1s 2s 2p
From the electronic configuration of an element, the electronic configuration of its ions can
be found and the method of expression of their electronic configuration is the same.
Remember: For transition metals, after filling electrons in 3d orbitals, the 4s orbital
becomes higher in energy than 3d orbitals.
Originally, energy of 4s < energy of 3d (∴ electrons enter 4s first)
Once 3d orbitals are filled with electrons, those 3d electrons will repel 4s electrons
further away from the nucleus.
Hence, the 4s orbital will be pushed to a higher energy level (> 3d)
As a result, in case of ionization, we start from 4s instead of 3d.
Examples:
1. Give the “electrons-in-boxes” diagram of Cu+ and Cu2+
2. Give the “electrons-in-boxes” diagram of Fe, Fe2+ and Fe3+. Hence, briefly explain
whether Fe2+ and Fe3+ would be more stable.
s-block p-block
d-block
f-block
In the Periodic Table, the elements are arranged in order of increasing atomic number.
A new row (period) is started when electrons start to enter a new principal energy level.
Elements whose atoms have a similar outer electronic configuration are placed in a vertical
column (group).
Metals: elements on the left of the Periodic Table
Non-metals: elements on the right of the Periodic Table
Metalloids (semi-metals): elements close to the zig-zag line (e.g. B, Si, As, etc.)
p-block elements (p 棟元素 ): Elements with valence electrons occupying the p orbitals.
Group III to Group 0 elements
Group VII (Halogens)
Group O (Noble gases)
Chemical behaviour in this block varies widely with the reactivity of the metals,
metalloids and non-metals, and the comparative lack of reactivity of noble gases.
Similarities within a group are shown by halogens and noble gases.
Group IV elements carbon to lead show a dramatic change in chemical properties
within a group (a transition from non-metal to metal).
f-block elements: Lanthanide and actinide series (inner transition elements), having f orbitals
occupied by electrons.
Lanthanides are widely spread throughout the earth’s crust in trace amount. They are
also known as ‘rare earth elements’ (稀土元素).
Actinides are all radioactive metals
There are many factors affecting the magnitude of the ionization enthalpy of an atom:
1. The electronic configuration of the atom
The atoms of some elements have half-filled or completely filled sub-shells
which give them extra stability. Larger amount of energy is required to ionize these atoms.
♦ When the atomic radius of an atom increases, the outermost shell electrons are
further away from the nucleus.
♦ Then the attraction that the electrons experience from the nucleus would be less.
♦ Hence, the ionization enthalpy becomes lower.
Discussion:
1. There is a general increase in 1st I.E. across both Periods 2 and 3:
Moving across a period, there is an increase in the nuclear attraction due to
the addition of proton in the nucleus. (原子內的核電荷隨著原子序的上升而增
加)
The added electron is placed in the same quantum shell. Thus it is only
poorly shielded by other electrons in that shell. (所加入的電子是進入同一電子
層,電子與電子之間的屏蔽效應較小)
As a result, there will be an increase in effective nuclear charge across the
period (有效核電荷隨之增加,故此第一電離焓逐漸增加)
Besides, going across a period, the atomic radii of elements decrease and
hence the size of electron cloud decreases.
As the electron cloud becomes closer to the nucleus, it becomes more
difficult to lose an electron.
7. There is a large drop in 1st I.E. when moving from one period to another.
The last element of each period has the stable noble gas electronic configuration
(ns2np6). The ionization enthalpy will be very high. (一個週期內的最後一個元
素有穩定的貴氣體電子排佈。電離焓極高。)
At the beginning of a new period, the additional s electron is added to a new
electron shell which is further away from the nucleus. (一個週期內的第一個元
素有 一 粒 額外 增加 的 s 電 子, 它離 原子 核 更 遠、 亦 會 被內 層的 電 子 遮
蔽。)
Also, this s electron is effectively shielded from the nucleus by the inner shells.
As a result, this outermost s electron is less firmly attracted by the nucleus and
easily removed, leading to a particularly low 1st I.E. in Group I elements.
8. 1st I.E. of Ne and Ar is maximum in the 2nd and 3rd period respectively
They have completely filled n = 2 and n = 3 electron shell respectively, which
they are most stable.
The following figure shows the comparison between 1st I.E. and 2nd I.E.
When an electron is added to an atom with a fully filled or half-filled outer subshell (e.g.
nitrogen), the 1st E.A. is less negative or endothermic since such electronic configuration
shows enhanced stability.
The halogens are expected to have the most negative 1 st E.A. because the addition of one
electron to the atoms leads to a stable noble gas electronic configuration.
1st E.A. of alkali metals usually close to zero or endothermic. This is due to strong shielding
effect of s-subshell.
The 1st E.A. is usually being less negative when going down a group. Take Group VII as an
example:
The 1st E.A. of O and S are exothermic because the attraction between the
incoming electron and the nucleus is stronger than the repulsion between the incoming
electron and the existing electrons.
The 2nd E.A. of O and S are endothermic because in the presence of the extra electron,
the extra electron charge offers a stronger repulsion with the incoming electron. Also,
the electron cloud of O– and S– will expand and the incoming electron will occupy a
position further from the nucleus which reduces the attraction with the nucleus.
In general, electronegativity values increase from left to right across each period
This can be explained in term of the increase in effective nuclear charge across a
period. Although an extra electron is also added for each element, this does not fully
shield the effect of the increase nuclear charge. An increase in effective nuclear charge
makes the attraction for the bonded electrons increase.
Electronegativity decreases when going down each group
This occurs because, in moving down a group, the screening of the atoms increases and
the attractive force of the shielded nucleus is therefore reduced.