Chemistry Unit 4
Chemistry Unit 4
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Sodium is eighth element following Lithium. Lithium, Sodium, and Potassium have
similar chemical properties.
Chlorine is the eighth element after Fluorine. The chemical properties of Fluorine
and Chlorine are similar
The limitations of this classification of elements were that:
i. The inert gases were not discovered till then.
ii. Beyond Ca, this repetition was not observed
iii. He assumed only 56 element existed in the nature
iv. He put two element in one slot in the column of unlike element having different
chemical properties
v. Iron was placed away from Co and Ni
4.2 Mendleev’s Classification of the Elements
The earliest version of the current form of periodic table was presented simultaneously by
Dmitri Mendeleev of Russia and Lothar Meyer of Germany. Both the scientists arranged the
elements in order of increasing atomic weights and observed that elements with similar
properties (in families) appeared at regular intervals.
4.2.1 Mendeleev’s Periodic Law
Mendeleev’s periodic law stated that the physical and chemical properties of
elements are the periodic function of their atomic weights.
In 1871, Mendeleev published a short periodic table which
1. Consisted of only 63 elements. Inert gases were not included as they were not
discovered at that time.
2. These elements were arranged in seven horizontal rows called as periods and eight
vertical columns called as groups.
3. Some vacant sites were specified for undiscovered elements and their properties
predicted. These were found true and verified when these elements were discovered
later.
Mendeleev’s periodic table was later modified after the discovery of inert gases
and several other elements.
The inert gases were placed in new Group 0.
Each long period was divided into two series, named as odd and even depending
on the serial number.
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The first seven elements formed the even series and the last seven elements
formed the odd series (not including the inert gases).
The vertical Groups I to VII were further divided into two subgroups A and B to
accommodate elements with difference in properties.
The elements of even series in the long periods were placed in subgroup A while
the elements of odd series were placed in the B subgroup.
The Group 0 was not split further and in Group VIII three sets containing three
elements each were placed.
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2. Group IIA elements are called as alkaline earth metals.
3. Group VB elements are called as pnicogens.
4. Group VIB elements are called as chalcogens.
5. Group VIIB elements are called as halogens.
6. Group 0 elements are called as noble (inert) gases.
The merits of Mendeleev’s periodic table are listed as follows:
1. The study of properties of elements became more systematic and easier.
2. There are several vacant positions from which the guidance of discovery of new
elements was found.
The demerits of Mendeleev’s periodic table are given as follows: Some of the elements
are wrongly placed though their atomic weights are larger compared to the next one.
For example, (i) Ar:40 (ii) Te: 127.6 (iii) Co: 58.9
K:39 I: 126.9 Ni:
58.6
4.3. The Modern Periodic Table
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4.3.1 The Periodic Law
According to the modern periodic law, the physical and chemical properties of
the elements are the periodic functions of their atomic number.
Note that the arrangement of A and B subgroups is different from that in the
modified form of Mendeleev’s periodic table.
The left and right corners of the table are assigned as sub-groups A and the
middle of the periodic table is assigned as subgroups B.
4.3.2 Groups and Periods
Many different forms of the periodic table have been published since
Mendeleev’s time. Today, the long form of the periodic table, which is called
the modern periodic table, is commonly in use.
It is based on the modern periodic law. In the modern periodic table, elements
are arranged in periods and groups.
Periods: The horizontal rows of elements in the periodic table are called periods or
series. Elements in a period are arranged in increasing order of their atomic numbers
from left to right. There are 7 periods in the modern periodic table, and each period is
represented by an Arabic numeral: 1, 2 . . . and 7.
Elements in the same period have the same number of shells.
Periods 1, 2, and 3 are called short periods while periods 4, 5, and 6 are known as
long periods.
Period 1 contains only 2 elements, hydrogen and helium. Period 2 and period 3
contain 8 elements each.
Period 4 and period 5 contain 18 elements each. Period 6, the longest period, has
32 elements. Period 7, 32 elements. Period 7 element is radioactive and/or an
artificial element.
Except for the first period, all periods start with an alkali metal and ends with a
noble gas.
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The arrangement of electrons in an atom is known as the electron
configuration of the atom.
Because atoms of different elements have different numbers of electrons,
a distinct electronic configuration exists for the atoms of each element.
Like all systems in nature, electrons in atoms tend to assume
arrangements that have the lowest possible energies.
The lowest energy arrangement of the electrons in an atom is called the
ground state electron configuration.
A few simple rules, combined with the quantum number relationships
discussed below, allow us to determine these ground state electron
configurations.
The quantum mechanical model is designated by the following notation: a
coefficient which shows the main energy level, a letter that denotes the
sublevel that an electron occupies, and a superscript that shows the
number of electrons in that particular sublevel. The designation is
explained as follows
For example, the electron configuration of lithium (53Li) is: 1s22s1. This
indicates that there are 2 electrons in the first s-sublevel and 1 electron in
the second s-sublevel. The configuration for sodium (2311Na) atom is:
1s22s22p63s1. This indicate that there are 2 electrons in the first s-sublevel,
2 electrons in the second s-sublevel, 6 electrons in the second p-sublevel,
and 1 electron in the third s-sublevel.
Example 4.1. Electronic configuration of 2311Na= 1s22s22p63s1(2, 8, 1).
Sodium has 3 main shells. Hence, sodium is found in period 3.
Example 4.2. By looking example above write the electron configuration of
9F and 17Cl. What are the similarities and differences in the electron
configuration of F and Cl?
Electronic configuration of 9F= 1s22s22p5 (2, 7) and the electronic
configuration of 17Cl= 1s22s22p63s23p5 (2, 8, 7).
Both have the same number of electrons in their valence shell.
Flourine has two shells whereas chlorine has three shells
Groups: are the vertical columns of elements in the periodic table.
There are 18 columns or groups in the modern periodic table.
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Group numbers are usually designated with the numbers I to VIII
each followed by the letter A or B.
These are:
IA . . . . . . . . . VIIIA Main groups (A groups)
IB . . . . . . . . . VIIIB Sub groups (B groups)
Elements in a given group have the same number of outermost shell electrons.
Elements in the same group have similar chemical properties. For the main group
elements the group number equals the number of valence electrons.
Example 4.3 Electronic configuration of 3517Cl = 1s22s22p63s23p5 (2, 8, 7).
The number of valence electrons of chlorine is 7. Hence chlorine is found in Group VIIA
4.3.3 Classification of the Elements
The assignment of all the electrons in an atom into specific shells or orbitals (s, p,
d, f ) is known as the element’s electronic configuration.
The elements can be arranged in the long form of the periodic table based on the
electronic configuration and classified as s, p, d and f-block elements.
1. s-block elements:
If the last electron enters into s-orbital, the elements are called as s-block
elements.
The general valence (outermost) shell electronic configuration is given by ns1−2 .
That means [IG] ns1 for Alkali metals and [IG] ns2 for Alkaline earth metals,
where IG represents the inert gas core.
2. p-block elements:
If the last electron enters into the p-orbital, the elements are called as p-block
elements.
The general valence shell electronic configuration is ns2 np1- 6.
The p-block elements are placed in Group number IIIA to VIIIA.
a. Valence shell electrons for s-block elements is equal to the number of electrons in
the s orbital having the highest principal quantum number.
b. Valence shell electrons for p-block elements are equal to the number of electrons in
the s and p orbitals having highest principal quantum number.
c. The total number of valence shell electrons is equal to its group number according to
A and B convention.
d. He (ns2) is excluded from p-block in terms of electronic configuration and it is better
to consider it as s-block element. But according to its chemical behavior it is justified to
place it in Group VIII.
3. d-block elements: If the last electron enters into d orbital, the elements are called d-
block elements (except Thorium). The general valence shell electronic configuration is:
ns0–2(n–1)d1–10 or ns1–2(n–1)d1–10 (except for palladium)
Total valence shell electrons of d-block elements = Total number of electrons in the
outermost shell (ns orbital) and penultimate shell [(n – 1) d orbitals].
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4. f-block elements: If the last electron of the elements enters into f-orbital, they are
considered as f-block elements. The general valence shell electronic configuration is:
2 0–1 1–14
ns (n–1) d( )(n–2)f( )
Total valence shell electrons = Electrons present in ns, (n – 1)d and (n – 2)f orbitals or
subshells.
4.3.4 The Representative Elements
The representative elements (also called main group elements) are the elements
in Groups IA through VIIA, all of which have incompletely filled s or p subshells of
the highest principal quantum number.
With the exception of helium, the noble gases (the Group VIIIA elements) all have
a completely filled p subshell.
(The electron configurations are 1s2 for helium and ns2 np6 for the other noble
gases, in which n is the principal quantum number for the outermost shell).
some main groups have traditional names and others as family of the first
member in the group which are often used in textbooks.
Group I – alkali metals, Group II – alkaline earth metals, Group III - boron family,
Group IV - carbon family, Group V - nitrogen family, Group VI - oxygen family,
Group VII – halogens Group VIII – noble gases.
A clear pattern emerges when we examine the electron configurations of the
elements in a particular group.
All members of the Group IA alkali metals have similar outer electron
configurations; each has a noble gas core and an ns1 configuration of the outer
electron.
Similarly, the Group IIA alkaline earth metals have a noble gas core and an ns2
configuration of the outer electrons.
The outer electrons of an atom, which are those involved in chemical bonding,
are often called the valence electrons.
Having the same number of valence electrons accounts for similarities in
chemical behavior among the elements within each of these groups.
This observation holds true also for the halogens (the Group VIIA elements),
which have outer electron configurations of ns2np5 and exhibit very similar
properties.
We must be careful, however, in predicting properties for Groups IIIA through VIA.
For example, the elements in Group IVA all have the same outer electron
configuration, ns2np4, but there is much variation in chemical properties among
these elements: Carbon is a nonmetal, silicon and germanium are metalloids, and
tin and lead are metals.
Elements in the same group have similar chemical properties because they have
the same number of valence electrons in their outer most shell.
Elements in the same period have different chemical properties because of
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regular increase in valence electrons in all the elements in the period.
4.4 The Major Trends in the Periodic Table
Periodic trends are patterns in elements on the periodic table.
Major trends are:
Electronegativity
ionization energy
electron affinity
Atomic radius and metallic character.
The existence of these trends is due to the similarity in atomic structure of the
elements in their groups or periods and because of the periodic nature of
elements.
The electron configurations of the elements show a periodic variation with
increasing atomic number.
Consequently, there are also periodic variations in physical and chemical
behavior. In this section and sections 4.5 and 4.6, we will examine some physical
properties of elements that are in the same group or period and additional
properties that influence the chemical behavior of the elements. First, let’s look
at the concept of effective nuclear charge, which has a direct bearing on atomic
size and on the tendency for ionization.
4.4.1 Atomic radius
For atoms linked together to form an extensive three-dimensional network,
atomic radius is simply one-half the distance between the nuclei in two
neighbouring atoms.
For elements that exist as simple diatomic molecules, the atomic radius is one-
half the distance between the nuclei of the two atoms in a particular molecule.
Within a group of elements we find that atomic radius increases with increasing
atomic number.
For the alkali metals in Group 1A, the outermost electron resides in the ns orbital.
Because orbital size increases with the increasing principal quantum number n,
the size of the metal atoms increases from Li to Cs even though the effective
nuclear charge also increases.
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Figure 4.6 Atomic radii (in picometers) of representative elements according to
their positions in the periodic table. Note that there is no general agreement on
the size of atomic radii. We focus only on the trends in atomic radii, not on their
precise values.
Example 4.4 Referring to a periodic table, arrange the following atoms in order of
increasing atomic radius: P, Si, N.
Strategy What are the trends in atomic radii in a periodic group and in a particular
period? Which of the preceding elements are in the same group? In the same
period? Solution From Figure 4.6 we see that N and P are in the same group
(Group VA). Therefore, the radius of N is smaller than that of P (atomic radius
increases as we go down a group). Both Si and P are in the third period, and Si is
to the left of P. Therefore, the radius of P is smaller than that of Si (atomic radius
decreases as we move from left to right across a period). Thus, the order of
increasing radius is N < P < Si.
Which atom is the smallest and which atom is the largest?
4.4.2 Ionization Energy
Ionization energy is the quantity of energy that an isolated, gaseous atom
in the ground electronic state must absorb to discharge an electron,
resulting in a cation. H(g) → H+(g) + e−
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This energy is usually expressed in kJ/mol, or the amount of energy it
takes for all the atoms in a mole to lose one electron each.
When considering an initially neutral atom, expelling the first electron will
require less energy than expelling the second, the second will require less
energy than the third, and so on.
Each successive electron requires more energy to be released.
This is because after the first electron is lost, the overall charge of the
atom becomes positive, and the negative forces of the electron will be
attracted to the positive charge of the newly formed ion.
The more electrons that are lost, the more positive this ion will be, the
harder it is to separate the electrons from the atom.
In general, the further away an electron is from the nucleus, the easier it is
for it to be expelled.
In other words, ionization energy is a function of atomic radius; the larger
the radius, the smaller the amount of energy required to remove the
electron from the outer most orbital.
Since going from right to left on the periodic table, the atomic radius
increases, and the ionization energy increases from left to right in the
periods and up the groups.
Exceptions to this trend is observed for alkaline earth metals (Group IIA)
and nitrogen group elements (Group VA).
Typically, Group IIA elements have ionization energy greater than Group
IIIA elements and group VA elements have greater ionization energy than
group VIA elements.
Groups IIA and VA have completely and half-filled electronic configuration
respectively, thus, it requires more energy to remove an electron from
completely filled orbitals than incompletely filled orbitals.
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Figure 4.8 Trend of ionization energy in kJ/mol of period 2 elements.
Alkali metals (Group IA) have small ionization energies, especially
when compared to halogens or Group VIIIA
The full positive charge of the nucleus is not felt by outer electrons
due to the negative charges of inner electrons partially canceling
out the positive charge, is called shielding.
The more electrons shielding the outer electron shell from the
nucleus, the less energy required to expel an electron from said
atom.
The higher the shielding effect the lower the ionization energy.
It is because of the shielding effect that the ionization energy
decreases from top to bottom within a group.
From this trend, Cesium is said to have the lowest ionization energy
and Fluorine is said to have the highest ionization energy (with the
exception of Helium and Neon).
Example 4.5 (a) Which atom should have a smaller first ionization energy: oxygen or
sulfur?
(b) Which atom should have a higher second ionization energy: lithium or beryllium?
Strategy (a) First ionization energy decreases as we go down a group because the
outermost electron is farther away from the nucleus and feels less attraction.
(b) Removal of the outermost electron requires less energy if it is shielded by a filled
inner shell.
Solution (a) Oxygen and sulfur are members of Group VIA.
They have the same valence electron configuration (ns2 np4 ), but the 3p electron in
sulfur is farther from the nucleus and experiences less nuclear attraction than the 2p
electron in oxygen. Thus, we predict that sulfur should have a smaller first ionization
energy.
(b) The electron configurations of Li and Be are 1s22s1 and 1s22s2, respectively.
The second ionization energy is the minimum energy required to remove an electron
from a gaseous unipositive ion in its ground state.
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For the second ionization process we write
+ 2+ – 2 1
Li (g) → Li (g) + e 1s 1s
+ 2+ 2
Be (g) → Be (g) + e– 1s 2s1 1s2
Because 1s electrons shield 2s electrons much more effectively than they shield each
other, we predict that it should be easier to remove a 2s electron from Be+ than to
remove a 1s electron from Li+
4.4.3 Electron Affinity
Electron affinity is defined as the change in energy (in kJ/mole) of a neutral atom
(in the gaseous phase) when an electron is added to the atom to form a negative
ion.
In other words, the neutral atom’s likelihood of gaining an electron.
Energy of an atom is defined when the atom loses or gains energy through
chemical reactions that cause the loss or gain of electrons.
A chemical reaction that releases energy is called an exothermic reaction and a
chemical reaction that absorbs energy is called an endothermic reaction.
Energy from an exothermic reaction is negative, thus energy is given a negative
sign; whereas, energy from an endothermic reaction is positive and energy is
given a positive sign.
When an electron is added to a neutral atom (i.e., first electron affinity) energy is
released; thus, the first electron affinities are negative.
However, more energy is required to add an electron to a negative ion (i.e.,
second electron affinity) which overwhelms any the release of energy from the
electron attachment process and hence, second electron affinities are positive.
First Electron Affinity (negative energy because energy released):
X(g) + e− → X− (g) (1)
Second Electron Affinity (positive energy because energy needed is more than
gained):
X− (g) + e− → X2− (g) (2)
Ionization energies are always concerned with the formation of positive ions.
Electron affinities are the negative ion equivalent, and their use is almost always
confined to elements in Groups VI and VII of the Periodic Table.
The first electron affinity is the energy released when 1 mole of gaseous atoms
each acquire an electron to form 1 mole of gaseous -1 ions.
It is the energy released (per mole of X) when this change happens.
First electron affinities have negative values. For example, the first electron
affinity of chlorine is -349 kJ mol-1. By convention, the negative sign shows a
release of energy.
When an electron is added to a metal element, energy is needed to gain that
electron (endothermic reaction).
Metals have a less likely chance to gain electrons because it is easier to lose
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their valance electrons and form cations.
It is easier to lose their valence electrons because metals’ nuclei do not have a
strong pull on their valence electrons. Thus, metals are known to have lower
electron affinities.
Example 4.6 Group IA Electron Affinities
This trend of lower electron affinities for metals is described by the Group I metals:
Lithium (Li): -60 KJ mol-1
Sodium (Na): -53 KJ mol-1
Potassium (K): -48 KJ mol-1
Rubidium (Rb): -47 KJ mol-1
Cesium (Cs): -45 KJ mol-1
Notice that electron affinity decreases down the group.
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Work sheet on Modern periodic table
1. The atom having the valence-shell configuration 4s2 4p5 would be in:
(a) Group VIA and Period 5
(b) Group IVB and Period 4
(c) Group VIB and Period 7
(d) Group VIIA and Period 4
(e) Group VIIB and Period 4
2. Select the term best describing the series of elements: Mn, Fe, Co, Ni, Cu.
(a) d-transition metals
(b) representative elements
(c) metalloids
(d) alkaline earth metals
(e) halogens
3. Which element has the largest atomic radius?
(a) Li
(b) Na
(c) Rb
(d) F
(e) I
4. 4. Which of the following terms accurately describes the energy associated with
the process: Li(g) Li+(g) + e-
(a) electron affinity
(b) binding energy
(c) ionization energy
(d) electronegativity
(e) none of these
5. The species that contains 24 protons, 26 neutrons and 22 electrons would be
represented by the symbol:
(a) 50V3+
(b) 26Cr2+
(c) 50Cr2+
(d) 50Mn2+
(e) none of these
6. Which element has the lowest first ionization energy?
(a) He
(b) Ne
(c) Ar
(d) Kr
(e) Xe
7. Which element has the highest first ionization energy? (Note: this is an exception
to the general trend - see notes- you may be responsible for this.)
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(a) Be
(b) B
(c) C
(d) N
(e) O
8. Which one will have the highest 2nd ionisation energy?
(a) 1s2 2s2 2p6 3s1
(b) 1s2 2s2 2p4
(c) 1s2 2s2 2p6
(d) 1s2 2s2 2p6 3s2
9. Which of the following order is correct for the first ionization energies of following
elements?
A) B < Be < N < O
B) Be < B < N < O
C) B < Be < O < N
D) B < O < Be < N
10.The electron configuration of elements A, B and C are [He]2s1, [Ne]3s1 and [Ar]4s1
respectively. Which one of the following order is correct for the first ionization
potentials of A, B and C?
A) A > B > C
B) C > B > A
C) B > C >A
D) C > A > C
11. Which of the following species has the highest ionization potential?
A) Li+
B) Mg+
C) Al+
D) Ne
12. Which of the following is the correct sequence for increasing order (i.e. smallest to
largest) of first ionization energy (IE1)?
A) O > C > F
B) O > N > F
C) N > C > F
D) F > N > O
13. How many periods and groups are present in the periodic table?
A. 7 periods and 18 groups
B. 8 periods and 7 groups
C. 7 periods and 7 groups
D. 8 periods and 8 groups
14. What is the other name for group 18th elements?
A. Noble gases
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B. Alkali metals
C. Alkali earth metals
D. Halogens
15. What modifications did early 1900s chemists make to Mendeleev’s periodic table?
A. They included chemical characteristics like bonding strength.
B. They also included material characteristics like melting point and density.
C. They arranged the elements using atomic mass rather than atomic number.
D. To arrange the elements, they used atomic number rather than atomic mass
16. Which of the following best describes the correct order of oxygen, fluorine, and
nitrogen’s atomic radii?
A. O < F < N
B. N < F < O
C. F < O < N
D. O < N < F
17. Which of the following elements has two shells, both of which are filled completely?
A. neon
B. calcium
C. boron
D. helium
18. The elements that do not normally form compounds are:
A.elements in the carbon family
B. metals
C. halogens
D.Inert gases
20. Which of the following does not decrease as one descends the group of the periodic
table?
A. Atomic radius,
B. metallic nature
C. number of atomic shells
D. valence electrons
21. Which changes in both charge and radius occur when an atom loses an electron?
A. A negative ion is formed with a smaller radius than the atom.
B. A negative ion is formed with a larger radius than the atom.
C. A positive ion is formed with a smaller radius than the atom.
D. A positive ion is formed with a larger radius than the atom.
22. The elements on the Periodic Table of the Elements are arranged in order of
increasing
A. atomic mass
B. atomic number
C. mass number
D. oxidation state
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23. Which element has chemical properties that are most similar to potassium?
A. calcium
B. cesium
C. nitrogen
D. sulfur
24. Magnesium and calcium have similar chemical properties because their atoms in
the ground state have
A. equal numbers of protons and electrons
B. equal numbers of protons and neutrons
C. two electrons in the first shell
D. two electrons in the outermost shell
25. Which ion has the largest radius?
A. Br-
B. Cl-
C. F-
D. I-
26. Which element is classified as a metalloid?
A. Cr
B. Cs
C. Sc
D. S
27. Arrange each set of elements in order of increasing magnitude of electron affinity.
A. Pb, Bi, and Te
B. Na, K, and Rb
C. P, C, and Ge
28. Arrange each set of elements in order of decreasing magnitude of electron affinity.
A. As, Bi, and N
B. O, F, and Ar
C. Cs, Ba, and Rb
29. Of the species F, O−, Al3+, and Li+, which has the highest electron affinity? Explain
your reasoning.
30. Of the species O−, N2−, Hg2+, and H+, which has the highest electron affinity?
Which has the lowest electron affinity? Justify your answers.
31. The correct increasing order of electron affinity among the following species:
a. O, S, Se b. Cl, F, S, O
32. The correct order of electron affinities of S, N, O and Cl is:
33. When an electron is added to a nonmetal atom, is energy released or absorbed?
34. Why do nonmetal atoms have a greater electron affinity than metal atoms?
35. Why are atoms with a low electron affinity more likely to lose electrons than gain
electrons?
36. As you move down a group of the periodic table, does electron affinity increase or
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decrease, if so, why?
37. Why do nonmetals want to gain electrons?
38. Why do metals have a low electron affinity?
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