Lecture 3

3
(a) (b)

Lecture 3 Objectives or Aims

period number

At the end of this unit you should be able to; arrange elements in the periodic table according to the group and discuss the periodicity of the periodic table

3.0

Introduction

We have just described the Aufbau principle of making probable assignments of electrons to the atomic orbitals !here are over "#3 kno$n elements %hemists have noted that many elements sho$ very strong similarities to one another &ecognition of periodic regularities in physical and chemical behaviours and need to organi'e the large volume of available information about the structure and properties of elemental substances led to the development of the periodic table---a chart in which elements having similar chemical and physical properties are arranged in groups (n this lecture you $ill learn ho$ to place elements in groups and periods

ACTIVITY i) ii) &ead about historical development of the )eriodic table* +endeleev,s )eriodic !able and active rule &ead about the American and -uropean periodic tables

(n high school you learnt the short form periodic table. $here elements are arranged in hori'ontals ro$s. called periods and vertical column called groups !he groups are numbered from ( to /((( (&oman numerals) !here are several controversies about the details of the periodic table that are still unresolved despite the table,s e0istence for more than a century 1or instance. there are three different systems currently used to designate the vertical groups in the periodic table. namely. the American. -uropean and the modern (nternational 2nion of )ure and Applied %hemistry (2)A% format We $ill only discuss the modern periodic table in this lecture

3.1.1 Modern Periodic Table - The Long For

" 3 3 6 8

-lements are arranged $ith increasing atomic number in ro$s (called periods) and columns (called groups) -lements in 4roups " and 3 are also called s block elements* valence electrons fill in s orbitals -lements in 4roups "3 to "5 are also called p block elements* valence electrons fill in p orbitals -lements in 4roups ". 3 and "3 7 "5 are called main group elements -lements in 4roups 3 7 "" are called transition metal because they have partially filled d orbitals -lements in 4roups 3 7 "3 are called d block elements because valence electrons filled in d orbitals

f block elements (also called Lanthanides and Actinides)* valence electrons filling in f orbitals

-lements in each group have similar valence7electron (electons in the outermost shell) configuration and therefore similar properties

Figure 3.!

!he structure of the periodic table (diagram from Atkins ; <hriver)

3.1.!

Cla""i#$ing the %le ent" into the Periodic Table

We $ill learn ho$ to get the period and group numbers of the elements !his can be done in three steps* i) Write the electron configurations for the elements. using the Aufbau principle !he period number is the largest principal =uantum number in the electron configuration !o get the group number. arrange the electrons in order increasing principal =uantum numbers. the group number is the sum of electrons after the last p9 to be filled > ?ut for period 3 and 3. the group number is obtained as @"#Anumber of outer shell electronsB !hus carbon and sulphur

are in group "6 and "9 respectively !his takes into account the d7 block elements in the short form periodic table

&%LF-T%&T '(%&TI)*& i) -lements C and D (not their actual symbols) have atomic number "3 and 53 respectively !o $hich period and groups do they belongE &olution !he electronic configuration of* C D C D "s33s33p93s33p" "s3s33p93s33p96s33d"#6p98s36d"#8p99s36f"68d"#9p3 the largest principal =uantum number . n. is 3 (mplying period 3 the largest principal =uantum number . n. is 9 (mplying period 9 4roup numbers C D -lectrons already arranged in ascending order according to the value of n Arranging electrons according to n "s3s33p93s33p93d"# 6s36p9 6d"# 6f"68s38p98d"#9s39p3 !he last p9 to be filled is 8p9 !he number of electrons after that isF"#A3A3F"6 (mplying group "6 <ince it belong to period 3 4roup number F"#A3F"3

)eriod numbers

ii) Gitrogen and <ilver atomic number : and 6: respectively !o $hich period and groups do they belongE

Figure 3.1 !he modern periodic table

3.!

Periodic Trend" o# Ato ic Para eter"

Atomic properties such as effective nuclear charge. atomic radii. ioni'ation energies. electron affinity and electronegativity are important in accounting for the chemical properties of an element

3.!.1 "

&hielding

(n atoms $ith more than one electrons. the effect of electron7electron repulsion depends on $here the various electrons are located in the atom

-lectrons in the outer shell (higher n) are pushed a$ay by electrons in the inner shell (lo$er n) As a result. the net nuclear charge (or effective nuclear charge. H eff) felt by an outer electron is substantially lo$er than the actual nuclear charge (H) We say that the outer electrons are "hielded from the full charge of the nucleus by the inner electrons

-lectrons in the same shell (same n) have an immediate effect in shielding the nuclear charge -lectrons in the outer shell (higher n) do not shield the nuclear charge from the inner electrons (lo$er n)

(n "I3#. <later formulated a set of rules for the e##ecti+e nuclear charge felt by electrons in different atomic orbitals based on e0perimental data !he effective nuclear charge H eff can be calculated by the follo$ing e=uation*

Heff F Hactual 7 < H* atomic number (number of protons); <* <later screening constant;

!he values of < are estimated as follo$s* Write out the electron configuration of an element in groups of * (1s), (2s, 2p), (3s, 3p), (3d), (4s, 4p), (4d), (4f), ( s, p) etc -lectrons $ith higher n do not shield those in lo$er n; < F # I# the electron in ,ue"tion re"ide" in an s or p orbital"-ach of the other electron in the same ns, np group. < F # 38 -ach electron in the (n - 1) shell. < F # 58 -ach electron in the (n - 2) and lo$er shell. < F " ## I# the electron in ,ue"tion re"ide" in a d or f orbital"* -ach of the other electron in the same nd, nf group. < F # 38 -ach electrons in the (n - 1) shell. < F " ##

%.a ple" %alculate the effective nuclear charge for the outermost electron in O0ygen 4iven* -lectron configuration of O* 1s22s22p4!

%alculate the effective nuclear charge on a 3d electron in a Gickel atom

4iven* -lectron configuration of Gi* 1s22s22p"3s23p"3d#4s2!

3.3

Periodic Trend in %##ecti+e *uclear Charge

?elo$ is a table of the values of effective nuclear charge (Heff) for s and p electrons in elements Li 7 Ge*

-lement

Li

?e

Ge

"#

"s

3 9I

3 95

6 95

8 9:

9 99

: 99

5 98

I 96

3s

" 35

" I"

3 85

3 33

3 58

6 6I

8 "3

8 :9

3p

3 63

3 "6

3 53

6 68

8 "#

8 :9

"

(n the same atom. each electron $ith different n and l values can have a different Heff because the repulsive effects due to the other electrons is different - g . the H eff for the ? atom* "s JJ3s J 3p and the si'e of orbitals is* "s KK3s K 3p

1or the same n and l value. Heff increase across a period (e g . from Li to Ge) as H increases As a result. the si'e of the orbital decreases (electrons gets closer to the nucleus) and the si'e of the atoms decreases - g the H eff for the 2p orbitals* ? K % K G K O K 1 K Ge and the si'e of the 2p orbitals is* ? J % J G J O J 1 J Ge

3./

&i0e" o# Ato " and Ion"

<ince electrons can only be located by probability. there is no real boundary to an atom &adii of atoms and ions are obtained e0perimentally from measuring bond lengths in molecules. metals and ionic crystals by C7ray diffraction

1. Co+alent radii rco+-

defined as the half7distance bet$een the nuclei of t$o atoms of the same element joined by a covalent bond - g . %l3* bond distance F "I5 pm. atomic radius of %l F ("I5)L3 F II pm

!. Van der 1aal radiu" r+d1

Mefined as the half7distance bet$een the nuclei of t$o non7bonded atoms or molecules Obtained from the closest approach bet$een t$o non7bonded atoms or molecules in the solid state - g . van der $aal radius of %l F "5# pm In general2 r+d1 3 rco+.

3. Ionic radiu"

defined as the distance bet$een the nuclei of adjacent cations and anions in a purely ionic lattice

(n general. ranions J rcov J rcation for any given element

Cation"- rGaA F ""9 pm; covalent radius rGa F "86 pm; WhyE 1rom Ga ("s33s33p93s") to GaA ("s33s33p9)* Heff increases since no of electrons decreases Anion"- the covalent radius r%l F I: pm; r%l7 F "9: pm; WhyE 1rom %l("s33s33p93s33p8) to %l7 ("s33s33p93s33p9)* Heff decreases since no of electrons increases

3.4

Periodic Trend in Ato ic 5adii

Acro"" a ro1. the atomic radius deceases because the n value for the outer shell remains the same but Heff is increasing o - g 1or ro$ stared by Ga outer shell is 3s ". 3s3. 3s33p". 3s33p3 N .3s33p9. atomic radius decreases (from Ga to Ar) because the H value is increasing and the added electron do not completely shield the increase in H

6o1n a group. the increase in Heff does not completely counteract the fact that the outer electrons are in orbitals $ith higher n. so radius increase do$n a group o - g 1or group headed by ?e outer shell is 3s 3. 3s3 . 6s3 . 8s3. 9s3. :s3 . atomic si'e increases from ?e to &a

!able 3 8 %ovalent radii (pm) of some selected elements

Li "33 Ga "86 O 3#3 &b 3"9 ?e 5I +g "39 %a ":6 <r "I" ? 53 Al ""5 4a "39 (n "66 % :: <i """ 4e "33 <n "6# G :: ) "#9 As "3# <b "6# O :3 < "#3 <e "": !e "39

Ato ic *u ber

3.7

Periodic Trend in Ionic 5adii

8oing do1n a group in cation" and anion" e g . +g3A(3s33p9)77J %a3A(3s33p9)77J <r3A(6s36p9)77J ?a3A(3s33p9) e g . 17(3s33p9)77J %l7(3s33p9)77J ?r7(6s36p9)77J (7(3s33p9) n value of outer orbital increase but not counteracted by the increasing Heff

&i0e o# i"oelectronic "erie" (ionsLatoms containing the same number of electrons)* e g . O37(3s33p9)77J 17(3s33p9)77J Ge(3s33p9)77J GaA(3s33p9) 77J +g3A(3s33p9) Heff increasing 77J <ince same no of electrons and H increasing &)O37)J r(17)J r(Ge)J r(GaA)J r(+g3A) (onic radii (pm) of some selected main group ions
LiA ?e3A O37 17

9# GaA I8 OA "33 &bA 365

3" +g3A 98 %a3A II <r3A ""3

Al

3A

"6# <37 "56 <e37 <n

6A

"39 %l7 "5" ?r7 (7 3"9

8# 4a3A 93 (n3A 5"

"I5 !e37 33"

:"

3.9

Periodic Trend in the Fir"t Ioni0ation %nerg$

!he ioni'ation potential of an atom is the minimum energy re=uired to remove an electron from a gaseous atom in its ground state !he magnitude of ioni'ation potential is a measure of the effort re=uired to force an atom to give up an electron. the higher the ioni'ation energy. the more difficult it is to remove the electron 1or many7electron atom. the amount of energy re=uired to remove the first electron from the atom in its ground state is called the #ir"t ioni0ation energ$ :I1; !he second ioni'ation energy ((3) and the third ioni'ation energy ((3) are sho$n in the follo$ing e=uations -nergy A CA (g) -nergy A C3A (g) C3A (g) A e7 C3A (g) A e7

Where C is the element and (g) denotes the gaseous state Pigher ioni'ation potentials labelled (3. (3. (6 and so on $ill correspond to the successive removal of additional electrons !he table belo$ gives the first ioni'ation energies of the first 3" elements

Table 3.9< Ioni0ation Potential :%nerg$; #or the Fir"t !0 %le ent"

= " 3 3 6 8 9 : 5 I "# "" "3 "3 "6 "8 "9 ": "5 "I 3#

%le ent P Pe Li ?e ? % G O 1 Ge Ga +g Al <i ) < %l Ar O %a

Fir"t "3"3 33:3 83# 5II 5#" "#59 "6## "3"6 "95# 3#5# 6I8 I :35 " 8:: I :59 3 "#"3 III 8 "38" "83" 6"5 : 85I 8

&econd 8365 :3## ":8: 363# 338# 359# 33I# 33:# 3I8# 689# "68# "53# "85# "I#6 338# 33I: 3999 3#83 ""68

Third

Fourth

Fi#th

&i.th

""5#5 "658# 399# 693# 685# 83## 9#8# 9"3# 9I## ::3# 3:8# 333# 3I"# 339# 353# 3I## 66"# 6I## 3#II3 38### 933# :8## :6:# 56## I3:# I86# "#8## ""9## 639# 6I9# 399# 8"9# 8::# 8I## 98## 335## 35### I6## ""### ""### "33## 336## "39## "65## "9### 936# 9II# 986# :36# 5### 5"## 6:333 83### "3### "83## "8### "99## "5### "56## 3#### 3"### 58## I3## 55## I9## ""###

(oni'ation potentials are positive =uantities (f the ioni'ation -nergy $as plotted against the atomic number. the periodicity $ill be clearly evident !he "st (oni'ation energy generally increases across the period 4roup ( elements (alkali metals) have the lo$est ioni'ation energies !his is because the elements have one valence electron that is effectively shielded by the completely filled inner shells %onse=uently. it is energetically easy to remove an electron from the atom of an alkali metal to form unipositive ion (LiA. GaA. OA NNNNN )

On the other hand non7metals have much higher ioni'ation energies !he ioni'ation energies of the metalloids usually fall bet$een those of metals and non7metals !his e0plains $hy metals readily form cations $hile non7metals form anions Po$ever. there are irregularities in the increase of the ioni'ation energy across the periods 1or e0ample going across group 3 to 3. thus from ?e to ? and from +g to Al !he group 3 elements have a single electron in the outermost sub level (ns3 np"). $hich is $ell shielded by the inner electrons and the ns3 electrons Less energy is therefore needed to remove a paired s electron from the same principle energy level !his brings about the lo$er ioni'ation energies in group 3 elements compared $ith those in group 3 in the same period )eriodic trends

Ato ic *u ber
1igure (oni'ation energies of the first 88 elements o (ncrease across each ro$. e g from Li to Ge; Ga to Ar; O to Or and so on (because $eff increases and the electrons in a given orbital are held more tightly, therefore, to remove the electron from the atom re%uires more energy)

o 4roup " Alkaline metals (i e Li. Ga. O. &b. %s and 1r) have minimum ( - (due to only single loosely held electron in the valence shell ns1) o 4roup "5 Goble gases (i e Pe. Ge. Ar. Or. Ce and &n) have the highest ( - (due to filled valence shell, ns2np"& high $eff valence electrons are tightly held) o +inor irregularity occur from group "3 to group "3 elements also from group "8 to group "9 elements* o - g ( - of ?e (5II 6 kQLmolJ( - of ? (5## 9 kQLmol)' due to completely filled ns2 configuration (3s3 in ?e vs 3s33p" in ?); o ( - of G ("6#3 3 kQLmolJ ( - of O ("3"3 IkQLmol)* due to half filled p orbital in ( (3s33p3 in G vs 3s33p6 in O); o ( - decreases do$n a group. e g LiJGaJOJ&bJ%sJ1r; PeJGeJArJOrJCeJ&n

o )ue to electrons filling in larger shell (larger n), further away from the nucleus! *herefore, valence electrons are well shielded from the nucleus by inner shell electrons and are loosely held! o !he ioni'ation energy increase only slightly across a ro$ in the transition or lanthanides an actinides series

&%LF-T%&T '(%&TI)*& i) ii) iii) -0plain $hy the first ioni'ation energy of phosphorous is higher than that of -0plain $hy the first ioni'ation energy of magnesium is higher than that of Why is the third ioni'ation energy of +g e0ceptionally higher than the second o0ygen aluminum ioni'ationE

3.>

Periodic Trend in %lectron A##init$

%lectron A##initie" !he electron affinity of an atom is defined as the energy change obtained $hen a neutral atom in the gaseous state captures an electron !hus. the energy is released by the reaction represented belo$* 7 C(g) A e7(g) RC7 (g) A energy (t is the reverse of the "st ioni'ation potential and may be looked at as the ability of an atom to accept one or more electrons !he largest electron affinities are those of the halogens !his is as e0pected since the addition of one electron yields the stable octet configuration of the "5 th group elements7the noble gases C is an atom of an element We assign a negative value to the affinity $hen energy is released !he more negative the electron affinity. the greater the tendency of the atom to accept an electron !he tendency to accept electrons increases as $e move from left to right across the periodic table !hus -lectron Affinity becomes more negative !he - A of metals are generally more positive (or less negative) than those of non7metals !he values differ little $ithin a group. but the halogens have the most negative - A values. $hile the noble gases that have filled outer s and p sub shells have no tendency to accept electrons !he - A of o0ygen has a negative value. $hich means that the process O (g) A e7 While that of the O7 is O7 (g) A e7 favourable in the gas phase O37 (g) is positive (:5#kjLmol) meaning that this process is not O7 (g) is favourable

3.?

Periodic Trend in %lectronegati+it$

%lectronegati+it$ @ !he tendency of an atom to attract electrons to itself in a chemical bond is referred to as electronegati+it$ !he greater the electronegativity of an atom. the more strongly the atoms attracts the electrons of a bond !his concept $as proposed by Linus )auling in "I3: -lectronegativity cannot be calculated accurately or measured directly Po$ever. $e e0pect it to depend on the magnitude of the charge and on the distance of the bonding pair of electrons from the nucleus !here are t$o important trends in electronegativity $ithin the periodic table* 7 (a) (b) nucleus ?ecause the electronegativity of an atom cannot be defined =uantitatively. it cannot be given a precise value but appro0imate values !able sho$s the electronegativity values electronegativity increases across a period as the charge increases electronegativity generally decreases from top to bottom in a group;

because $ith each successive shell. the bonding electrons are further from the

Table< %lectronegati+it$ @ o# "o e ele ent"

4roup )eriod " 3 3 6 8 " P 33 Li "# Ga "# O #I &b #I ?e "8 +g "3 %a "# <r "# ? 3# Al "3 4a "5 (n "8 % 38 <i ": 4e 3# <n ": G 3" ) 3" As 33 <b "5 O 38 < 36 <e 38 !e 3# 1 6" %l 35 ?r 3: ( 33 3 "3 "6 "8 "9 ": "5 Pe 7 Ge 7 Ar 7 Or 3" Ce 36

(ncrease of electronegativity77777777777777777777777777777777777777777R I portant application- Could u"e @ to e"ti ate bond polarit$ Atoms $ith similar electronegativity ( # 6 ) form non7polar bonds Atoms $hose electronegativity differs by more than 3 form ionic bonds Atoms $hose electronegativity differs by less than 3 form covalent bonds

3.10

Co

on ).idation &tate o# the %le ent"

O0idation number is the apparent charge assigned to an atom in a molecule or in a compound <ome o0idation numbers are fi0ed*

-lements O P 4roup " metals 4roup 3 metals Palogens

O0idation number 73 e0cept in pero0ide A" e0cept in hydride A" A3 7" e0cept in o0ygen compounds

3
" 3

&(MMA5Y

!he e+perimental basis of the periodic table of the elements is periodic la$* %ertain properties recur periodically $hen the elements are arranged by increasing atomic number !he theoretical basis is that the properties of an element are related to the electron configuration of its atoms. and elements in the same group of the periodic table have similar electron configuration