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    Periodic Table DISCLAIMER “The content provided herein are created and owned by various authors and licensed to Sorting Hat Technologies Private Limited (“Company”). The Company disclaims all rights and Liabilities in relation to the content. The author of the content shall be solely responsible towards, without limitation, any claims, liabilities, damages or suits which may arise with respect to the same.” Periodic Table Introduction: Itis quite natural to begin your study of inorganic chemistry with the study of the periodic table in this unit. Periodic table helps us to undergo a systematic study of the various elements found in nature, without which it would have been impossible for us to study all the elements. Qi] Why do we need to classify olements? Sol: Year Number of elements discovered 1800 31 1865 63 At present ne It is very difficult to study all the properties of such large number of elements individually. So scientists searched for a systematic way to organise these elements. (> What is periodic table? Sol; Periodic Table is a systematic arrangement of all the elements known to us accordance with their increasing atomic number and recurring chemical and physical properties. They are arranged in tabular form to keep similar property elements in vertical column (known as groups). Horizontal rows are known as periods. Genesis of Periodic Classification: (i) Dobereiner's Law of Triads: He formed group of 3 elements in such a way that, when the elements are arranged according to increasing atomic mass, then atomic mass of middle element is average of atomic masses of first and last element He found that elements of such groups have similar properties. Such groups were known as Dobereiner's Triad. Mathematically: If elements A, B, C have atomic masses x, y, 2 respectively, then ( xi2 }. also A,B.C have similar properties. cf , Na(A=23), K(A=39) 7+39 eg: atomic mass of Na = 23 = = average of atomic masses of Li and K Moro examples of Dobereiner’s Triad: Ca(A=40), Sr(A=88), Ba(A=137) Trick : If atomic numbers of elements A,B and C are xy and 2, and (y-x)= (z - y), then A,B and C are in triad. (no need of atomic mass). eg: Liz = 3),Nal 9), Dobereiner’s Triad > 1-3=19-11-=8 Caz = 20} Dobereiner Drawbacks: He wasn't able to classify all the known elements into triads. Properties of elements of different triads can’t be compared with each other. He made some triads based on similarities of properties but do not follow average of atomic mass rule, such a (HARI ), Na(A=23) 2341 eg: Average = = 12 # atomic mass of Li (i) O(A = 16), S(A = 32), Se(A = 79) 16479 Average= = 47.5 + atomic mass of S 5 Atomic weight of an clement xis 39, and that of element 2 is 132, an atomi "weight of their intermediate element Y, as per Dobereiner’s Triad, will be? (A) 88.5 (8) 93.0 (c) 171 (D) 85.5 Given elements X ¥ Z ne x According to Dobereiner’s Triad = oe =Y Q4 Sol: Sol: Qs Sol: _ 394132 2 =i 2 = 85.5 So, Atomic weight of Y = 85.5, The law of triads is applicable to a group: (@)C,N,O (HON (©) Na, K, Rb (0) Cl, Br, | D For Cl, Br. I 36.5 eso 512280 So, the law of trades is applicable only cl, Br, | Predict the approximate density of Cs from the following data using law of triad. K = 0.868 g cm™; RI 532 gem; Cs= 7? dea +6 2 Atomic number of K = 19, Rb = 37 Cs = 55 4, = 2d, 4, =2x1532-0.868=2.196 = dp, The b.pt. of Kr and Rn proximate b.pt, of Xo. 152°C and -62°C respectively. Calculate the .pt.of kr +b.pt. of bptof xe -BPLOFKr bt offin 2 7152-62 =a 2 107°C. Gi) A.E.B. de Chancourt He attempted to classify elements in order of increasing atomic weight and made a cylindrical table which was used to display periodic recurrence of properties. Drawback: He only published his paper but did not-publish his actual graph with irregular arrangements (©) The telluric helix was given by: (A) Dechan Courtois (8) Newlands (©) L. Meyer (D) Mendeleev Sol: 4 Telluric helix was gives by Dechan Courtois . Telluric helix is 16 equal lines and elements arrange in atomic weight Gi) Newland’s Law of Octaves: He arranged the elements in increasing order of their atomic weights and observed that every eighth element had properties similar to the first element just like every eighth note that resembles the first note in octaves of music. Do Re Mi Fa So La Ti li Be B C N OO F Na Mg Al Si P S$ Cl K Ca --- Drawbacks: His Law seemed to be true only for elements upto calcium. Until then noble gases weren't discovered. After discovery of noble gases, his law was modified. That is, properties of every ninth element are similar to properties of first one. (iv) Lothar Meyer's Curve: He plotted the physical properties such as atomic volume, melting point and boiling point against atomic weight and obtained a periodically repeated pattern. He observed that elements having similar properties occupy similar positions. In the following graph of atomic volume vs atomic mass, he observed that : i) Alkali metals occupy maxima of curve. ii) Alkaline earth metals occupy midpoints of descending curve Halogens occupy midpoints of ascending curve. Heavy Metals occupy minima of curve. ‘Aiomic mass Drawbacks: Graphical method was difficult to study. He also developed a table but before he got it published, Mendeleev’s Periodic Table was already published It was difficult to find similar positions on a curve of different properties as periodicity and nature of graph was not similar. (v) Mendeleev’s Periodic Table: He was responsible for publishing the Periodic Law for the first time. It states as follows: “Atomic mass is the fundamental property of elements and all other physical and chemical properties are periodic function of atomic mass.” He fully recognised the significance of periodicity and used broader range of physical and chemical properties to classify elements. His main basis was the similarities in empirical formulas and properties of compounds formed by the elements. Characteristics: He arranged 63 known elements into: 12 horizontal rows = series @ vertical columns = Groups. Groups were further divided: Subgroup A: Normal Elements. Subgroup B: Transition elements. Some of 12 series were grouped horizontally, these horizontal groups were known as periods. (7 periods) The Vill group consist of 9 elements in three vertical columns. Meri He classified all known elements into groups according to their similar properties. Hence, study of elements was made easier due to tabular classification. He realised that some elements did not fit in right place according to other properties, if placed according to atomic weight. So he ignored atomic weights, thinking that measurements might be incorrect. Hence, led to corrections of atomic weights of some elements : : U, Be, In, Au, Pt. ‘As he arranged elements with similar property, he considered that some elements were still undiscovered, and left several gaps, which helped in discovery of new elements. Eka Aluminium(Al) > Ga__ (Aaloo - Galoo) Eka Silicon( > Ge (Sita - Geeta) Eka Boron (6) > Sc (B.Se) > Eka Manganese(Mn) Te (MTech) Demerits: Position of Hydrogen was not fixed. Position of isotopes was not clear. He could not explain cause of periodicity. Some pairs of elements do not follow the increasing order of atomic weights, known as Anomalous Pairs. Te, 1 Co, Ni) (Th, Pa 1278 127) (58.9 58.6) (232 231, 5 Which main group elements have a different number of outer most electron "than its group number of Mendeleev’s periodic table? Sol; The noble gases group zero, they have 8 valence electrons. (Vi) Modern Periodic Law & The Modern Periodic Table: Henry Mosley's Experiment! Mosley measured frequency of x-rays emitted by metal. whenitis bombarded with high speed e- and plotted these two graphs: ‘Atomic mass ‘Atomic number He observed that the plot of ¥v vs ato mass is approximately a straight line but Vv vs atomic number is perfectly a straight line. So, He concluded that instead of atomic mass, atomic number should be fundamental property. Neils Bohr considered Mosley's suggestion and modified Mendeleev's periodic law, to give: Modern Periodic Law: “Atomic Number is the fundamental property of elements and all other physical and chemical properties are periodic functions of atomic number” Modern Periodic Table / Long form of Periodic Table : Modern periodic table is constructed on the basis of modern periodic taw and electronic configuration. t consists of : 18 vertical columns > Groups T horizontal rows = Periods Number of elements = 118. Orbitals filled in ‘n®” perio: (ns) ...(n-3)g, (n-2)f, (n-1)d, np Number of elements in ‘n™ period: Period —_arbitals filled No.ofelements _type of period 1 1s 1x2=2 shortest 2 28,2p 4x2=8 short 3 3s, 3p 4x2=8 short 4 48,30, 4p gx2-18 long 5 584d, 5p 9x2=18 long 6 6s, 4f. Sd. 6p 16 x2= 32 longest 7 78, Sf, 6d, 7p 16 x2= 32 longest Magic Nos.t Mathematically: Number of elements in n" perio nay 2 f nis even 2 2 (PH) If nis odd squawojo Uojsue.] J0UUI-} 10, LPO AS | SLPS | SLPHIS | SLPIaIS | SLPOIS | SL PRAT a on PW ws 3 no 0h, zon tor 001 66 86 SLePOdS | $L,P9,45 | SL,P9,IS | SLoPOIS | -SL,POJS | SL,PO4S | SL,PO4S | -$LP9IS 48 wo wy d an a ed WL SL, Goneral electronic configuration : ns? 38° |3s* > Goneral oxidation state of group-1 and group-2 is +1 79 | 20 and +2 respectively. K | ca > Larger in size, ela “+ Soft metals and silvery white in colour 37 | 38 rb | sr Mostly forms ionie compound. 5s" | 5s? + Have low IP and highly reactive. 35 | 56 0, never found in pure form. S| strong reducing agents 6s’ | 6s? 34 a7] eo > Gives flame test (except Be and Mg). Fr | Ra 7s' | as? (2) p-block: Elements in which last e” enters in p-subshell of valence shell, are placed in p-block. General E.C, ns’ np'* + seblock elements and p-block ‘oloments together known as Representative elements or Main Group Elements. > Good oxidising agente > Mostly forms covalent bonds. + Harder and heavier than s-block elements and have high EA. p-block elements are mostly non-metals and metalloids but few are Metals. (Metalloids —>Ge, As, Se, Te, Sb) H, N, 0, F, Cl and noble gases exist in gaseous form at room temperature. Br is the only non-metal which exist in liquid form. Grp 15 - Pictogens: refers to choking / suffocating property Grp 16 - Chalcogens: ore forming elements. Grp 17 - Halogens: sea-salt forming elements. Grp 18 - Noble / inert gas: Chemically inert elements. (3) d-block:- Elements in which last e” enters in d-subshell of penultimate shell are placed in d-block. a v Transition series | | nv | ome ‘Sa seria dit | sete | ae | ater | ae wo fa) a a, o 2 Transition series | ¥ | & | nw”) mo’ te 4d-series 2" Transition series 5d-ceries 4” Transition series 6d-series 4 Exceptions of (n+l) rule not Transition Elements 13, General electronic configuration ns*(n - }d°" All d-block elements except graup-12 elements are known as transition elements. Transition Elements: Elements with incomplete d-subshell of penultimate shell, either in ground state or stable oxidation state. Ali d-block elements are hard metals, hence show all properties of metals ~ good conductor of heat and electricity, malleable, ductile, sonorous ete. They have variable oxidation state due to less energy gap between (n-1)d and ns subshells. They mostly form coloured ions and show paramagnetism. Coinage Metals - Cu, Ag, Au Noble Metals - Au, Pt (4) f-block: Elements in which last eventers in f-subshell of anti- penultimate shell, are placed in f-block. lartnan in All F-block elements belongs to group- with 32 elements. General electronic configuration -sns?(n—1)d°"(n-2)f=* These are also known as Inner Transition Elements, as they are positioned between transition elements. ‘Pm’ among Lanthanoids and all Actinoids are radioactive. Elements having atomic no. (Z) greater than U (Z = 92), are man-made and termed as Transuranic elements. General stable oxidation state of f-block elements is +3, but lanthanides also show +2 & +4, while Actinides show +3, +4, +5, +6, +7 Lanthancids are also known as rare earth elements Metals, Non-Metals and Motalloids: , hence group - 3 is longest group Metals Non-Metals Metals are hard and are usually solid at room | They are usually soft and gas or solid at temperature (Hg is liquid at 25°C) room temperature (Br is liquid at 25°C) They are malleable and ductile They are brittle 14. Metals Non-Metals They are sonorous They are non-sonorous Good conductors of heat and electricity They are bad conductors (except : graphite) They have high melting and boiling point They have low melting and boiling points High tensile strength Low tensile strength Metallic character in periodic table 1n period : Left to right decreases ‘n group: tap to bottom increases Metalloid ements that show properties of both metals as well as non- metals are metallcids or Semi-Metals. Positioned between metals and non-metals. (Ge, As, Se, Te, Sb) Sol: Qn Sol: How many elements are yet to be discovered to complete the last the periodic table? What shall be the atomic number of the last member of the last period and te which group it shall belong? 13 elements, 118, zero group Why are the elements having ns’, np‘ configuration called inert? The elements having ns’, np* configuration have complete octet and thus neither possess the tendency to donate electron nor to accept electron and are thus stable. ‘There are only 14 lanthanoids and only 14 actinoids. Why? Lanthanoids and actinoids are the elements in which differentiating electron enters in to (n-2) f-subshell. Since ‘f’ subshell can accommodate a maximum of 14 electrons and thus number of lanthanoids and actinoids are 14. 6. Sol: Qis Sol: 3d, 4d and Sd series consists of 10 elements each. Explain. In 3d, 4d and 5d series, the differentiating electron enters to (n-1) d-subshell. ‘The maximum capacity of d-subshell is of 10 electrons. Thus, there are 10 elements each in 3d, 4d and Sd series [(n-1) d™™. ‘There are 2, 8 and 8 elements in first, second and third periods of periodic In first period 1s is completed. its capacity is of two electrons. in second period 2s 2p and in third period 3s 3p are completed. The capacity of these shells is of 8 electrons each. Thus, 2, 8 and 8 elements are present in first, second and third periods respectively. What is the atomic number of the element having maximum number of un- paired 2p electrons. To which group it belong? 1N. it belongs to 15 (or V A) group. ig electron enters in case of inner (n-2) f-subshell. Why is argon (at. wt. 39.94) placed before potassium (at. wt. 39:10) in the periodic table? ‘The periodic table is based on atomic number and the atomic number of Ar is 18 which comes first as the at. no. of K is 19. 16. Qi7 Sol: Qis Sol: Qi19 Sol: Boron is metalloid. Comment. It shows the metallic as well as non-metallic nature. ‘Sodium is strongly metallic, while chlorine is strongly non-metallic. Explain. ‘Sodium (ns!) has low IE and thus possesses strong tendency to lose electron and exhibits strong metallic nature, On the other hand chlorine (ns? np*) pos sesses high electron affinity and thus shows more tendency to accept elec tron to show strong non-metallic nature. Why are metals good conductor of current? Metals have low ionisation energies and so valence electrans form an ocean of loosely bonded electrons. These loosely bonded electrons are responsible for conduction of current in metals. Why are inert gases mono-atomic? Inert gases have complete octet (ns?, np*) and so do not form bonds. Why are the f-block The differentiating electron enters to in (n-2) f-subshell and thus elements are called ‘f-block elements. 7 Sol: Sol: Why are s-block elements most reactive? Because of low IE values, s-block elements possess more tendency to lose electron and are thus more reactive. | Why are zero group elements called noble gases or inert gases? These possess ns’ np* configuration and are thus chemically inert. How many elements out of first 100 elements possess 3d electrons? 80 (since filling of 3d-orbital starts from elements with at. no. 21). By examining the modern periodic table, find as many examples as you can of the violation of Mendeleev's periodic law that the chemical and physical properties of elements are periodic function to their atomic weights. Exceptions to Mendeleev's periodic law: CO and K ; Co and Ni, Te and I: Th and Pa: U and Np: Pu and Am. If placed in order of increasing atomic weight, these elements would not fall in the group with which they have similar properties. Why is the third period contains 8 elements and not 18 The filling of electrons in third period begins from 3s' and completes at 3p*. 8. Sol: Sol: Sol: Arrange the following pure solid elements in order of their increasing elec- trical conductance at room temperature: Ge, Ca, $ and $i : Also explain the S < Si < Ge < Ca; Metals are good conductor of current and non-metals are poor ones. Metallic character decreases from left to right across a period and from bottom to top in a group. Arrange the following elements in order of inereasing melting point and give reason. AL, F, Naand Mg. F < Na < Mg 100: Digit o |1 |2 |3 |4 5 6 |7 8 9 Nomenclature | nil [un [bi | tri [quad | pent | hex | sept | oct | enn symbol ee ee ee ee Pp hs o le Atomic No. _| IUPAC Name ‘Symbol ElementalName —_| Symbol 101 Unnitunium unu Mendelevium Md 102 Unnilbium Unb Nobelium No 103 Unnittrium: Unt Lawrencium ur 104 Unnitquadium Ung Rutherfordium Rf 105 Unnilpentium Unp Dubnium Ob 106 Unnithexium Unh Seaborgium Se 107 Unnitseptium Uns Bohrium 8h 108 Unniloctium Uno Hassium Hs 108 Unnilennium Une Meitnerium Mt no Ununnitlium vun Darmstadtium Ds 20. Atomic No. | IUPAC Name symbol Elemental Name _| Symbol ™ Unununnium uu Rontgenium Rg 12 Ununbium ub Copernicium cp 13 Ununtrium vat Nihonium Nh na Ununguadium uug Flerovium FL ns Ununpentium uup Moscovium Me ne Ununhexium Uuh Livermorium Ww "7 Ununseptium Uus Tennessine Ts ne Ununoctium Uuo ‘Oganesson og Group, period, Block identification: (a) If electronic configuration is given: Block: given by subshell in which last e enters. Period: largest principle quantum no. Group: If it belongs to ‘n®™ period and s-block, then group no. = no. of ns e” p-block, then group no. = 10 + no. of (ns + np)e~ d-block, then group no. = no. of (ns + (n - 1) de" f-block, then group no. = 3. @.g.: Br(Z = 35): 1s’ 2s? 2p°3s"3p"4s"3d"4p* Block = p-block (-" last e- enters p-subshell) Period = 4 ( largest quantum no. is 4) Group = 10 + no. of (4s + Ape" 210+ (245) (b) if atomic no. (Z) is given Block: Atomic no. of noble gas (x) = 2, 10, 18, 36, 54, 86, 118 s-block: Z = (x #1), (x + 2) p=block: Z = (x), (XI), (X-2), (4-3), (4), (%+5) f-block: Z = (68 to 71) & (89 to 100) d-block: Z = rest all Period: period of next noble gas Group: 18 + given atomic no.(Z) - atomic no. of next noble gas, Block Period Group s 3 18412 -18=2 p 2 1849-10-17 qd 4 18421-36=3 p44 18 + 33 - 36 = 15 a 65 18448 -54=12 f 6 3 Pp o7 18 +118 - 18 = 18 f 6 3 (ix) Z=74 d 6 18 +74- 86=6 @) 2=81 Pp 6 18+81-86=13 (xi) [Ar]3d54s? d 4 245=7 (xii) [xel6s" s 6 1 (xiii) [Kr]4d°58°5p? pS 10+242=14 (xiv) [xe]4f50'6s? f 6 3 (xy) [xe]5d°6s" ao 6 " > Calculate maximum no. of elements which can be present in the 9** period of periodic table. Sol: Method 1: Types of orbitals filled in 9" period: Ss 6 7f 8d Sp 4 + + + + No. oforbitals= 1+ 9+ 7+ 5+ 3=25 No. of elements = no. of em= 2 x 25 = 50 Method 2: 2 No. of elements = (2) ( nis odd) tg) ‘Some important points about Modern Periodic Table Diagonal Relationship : due to same icnic potential there are three pairs which have similar properties with diagonal element to each other. They are: (Li Mg),(Be © Al),(8 © Si) 50 22. Bridging elements : Period 3 elements are known as bridging elements as they have valencies similar to subgroup A & subgroup B (according to Mendeleev) Typical elements : Period 3 elements are known as Typical elements as they represent most of the properties of the elements of their respective periods. ‘Transuranic : Uranium (Z = 92) is last naturally occurring element, all elements with atomic no> 92 are man made and are known as Transuranic elements, Periodic Table (at room temperature) has : 14 Gaseous Elements : H, N, 0, F, Cl, He, Ne, Ar, Kr, Xe, Rn 2 liquid elements : Hg (Metal) + Br (non-Metal) Effective Nuclear Charge (Z,, or Z*): In multielectron species, electrons experience lesser attraction than number of protons present in the nucleus. The decrease in force of attraction is due to inner shell electrons, which is called as screening effect or shielding effect. Decrement in net force of attraction results in decrement in nuclear charge experienced by outer shell e*, Net nuclear charge experienced by outer most shell eis called effective nuclear charge (Z*) 2 = (2-6) where, 2 = nuclear charge 2* = effective nuclear charge « = screening constant or shielding constant. Characteristics of screening constant (0): Screening will be caused by same shell e~ or inner shell electrons only. None of outer shell electrons offer screening to inner shell electrons. Electrons closer to nucleus offer more shielding, it is known as penetration effect. Screening offered by & screening offered by e >L>M>N.. s>p>d>f... (fora particular shell) Theoretical calculation of screening constant (c): SLATER’S RULE: a Write electronic configuration in expanded form @ Rearrange the electronic configuration as follows: (1s)(282pX(3s 3p) (2¢) (48 4p) (44) (44) (Ss Sp) (Sd) (5F) ... (3)(@)__ Ifo on e of ns or np is calculated: [O} 6 for each e of ns and np (other than 1) is 0.35, Gi) for each & of (n ~1) shell is 0. 85 Gill) for each e° of (n-2) shell and inner shell is 1 (iv) for each 2° in outer shell of ns and np is 0. (6) If. on e- of nd or nf is calculated: @ for each e° of nd or nf (other than 1) is 0. 35 ii) for each e* on LHS of nd or nf (all inner e-) is 1 Gil) for each e* on RHS of nd or nf (all outer e* ) is 0 @.g.: Find Z* on valence e of Nitrogen (Z= 7) N: 18725? 2p? (182) (28*2p°) o=2%*085+4%0.35 o=17 +14 o23.1 2* = (2-0) = (7 - 31) z*=3.9 otal Same attraction from nucleus | How do atomic sizes vary in a group and in a period? Give reasons for the variations. Sol: Atomic size decreases along the period due to increase in effective nuclear charge as valence shells are more effectively pulled towards nucleus. On the other hand atomic size increases down the group due to decrease in effec tive nuclear charge. 24, Find 2* on (i) 4s, (ii) 3d, 3p, (iv) 3s electron of Fe. Sol: @ 48 of Fe. ((8”) (28?2p*) (38”3p*) (3d°) (487) 6 = (10 x1) + (14 x 0.85) + (1 x 0.35) = 10 +119 + 0.35 = 22.25 Z* = 26 - 22.25 = 3.75 (il) 3d e- of Fe. Fe : (1s?) (28? 2p") (3s? 3p%) (3d) (487) o = (18 x1) +6 x 0.35) +0 o = 18 +175 = 19.75 Z* = 26 - 19.75 = 6.25 (ili) 3p e- of Fe Fe : (1s?) (26? 2p") (3673p (349) (45) = 2%1+8x 085 +5 x 0.35 o= 246.8 +175 = 10.55 Z* = 26 - 10.55 = 15.45 (iv) 3s e- of Fe. Fe : (Is?) (28*2p% (38"3p*) (304) (48°) o=2*1+8*085+5% 0.35 o=246.8+175 2* = 26 - 10.5: Find Z* on valence electron of Li, Na, K and Mg. y Lit s%) (2s!) Sol: G= 2% 0.85 +0% 0.35 =17 Zeea-17213 K : (1s*) (2s'2p%) (38°3p9 (4s") o=10x148x085+0=168 Z* 219 - 16.8=22 Na: (1s*) (28? 2p9 (38") 6 =2%1+8* 085 +0 x 0.35 = 88 Zt =~ 8.8=22 Mg : (1s?) (28? 2p*) (387) 6 = 2% 148x085 +1 x 0.35 = 915 Z* 312-915 = 285 Observation of slater: @ = 2* increases by 0.65 in a period in 2 and 3” period. SR 8 HIS 8 Si 2nd— Li Be B c N O° F Ne 13 tes 26 325 39 ass 6 ses a NN PRON ON 3rd—» Na 22 285 35 415 47 535 60 665 Gi) 2* increases by 0.9 in a group on moving 2 to 3” period. ) 2: *) 23 °) Ds ) 2) Na‘ 2.2 285 a 4.18 “7 5.35 50 6.65 Z* remains constant in a group on moving 3 to 7™ period in s-block. constant = 2.2 285 | Constant = 285 Ba | 2.85 | Ra | 1 285) Gv) in two electron species like, He, Li’, Be”, etc., screening constant of one electron for another is 0.30. 2 In He(1s°), 0.3 (and not 0.35) -0.3 = 17 (and not 1.65) 26, (¥) According to slater, « and hence Z* on ns and np electron is same. e.g: Z* on 3s e° of Fe = Z* on 3p e- of Fe = 15.45, Practical observation of effective nuclear charge (Z,,) 1 a period, on moving from left to right number of proton increases by 1 and effect of proton is 100%, while no. of electron increases by 1 but effect of electron is less than 100%, (since e- is movable). So, overall as atomic number (Z) t Z,, +. Also, number of shell remains same and Z,,, % so, force of attraction (F,)+ (Left to right). na group, on moving top to bottom: (a) ns-block, Z,,, increases slightly. So, increase in shell no.(n) dominates small increase in 2, hence, force of attraction (F,) decreases down the group. (b) in d-block, Z,,, rapidly, due to poor shielding d and f electrons”. s0, large increase in Z,, dominates increase in shell no.(n) hence force of attraction (F,) increases down the group. (€) in p-block, initially Z,, increases rapidly due to less number of p-electrons and large number of d and f electrons. So, large increase in Z,,, dominates increase in shell no.(n) hence, F, increases down the group, initially in p-block. But later from (9 to p*) in p-block, number of p-electrons increases and no. of d and f-electrons remains same, so Z,, increases slowly. so, increase in shell no(n) dominates small increase in 2, Hence, F, increases down the group, later in p-block. Periodic trends in Property of elements: () Atomic Size: Theoretically, atomic size is the shortest distance between nucleus and outermost electron of an isolated gaseous atom. Outermost shell Actual radius tis difficult to measure the atomic size practically, because: 22. @ Existence of isolated atom is difficult. Gi) Position of moving electron cannot be predicted accurately. (Heisenberg's uncertainty principle). Therefore, determination of atomic size is done by calculating half of the internuclear distance between two atoms of an element. Based on the nature of the element and chemical bonds present with in them, different type of radius are defined : (1) Covalent radius (for non metals) (2) Metallic radius (for metals) (@) Vander waal’s radius (for Noble gases) 1. Covalent Radius: Covalent radius is half of internuclear distance between two singly bonded homo atoms. Three types of covalent radii can be given between two homo atoms Single bonded covalent radii (SBCR) = half of singly bonded homo atoms Double bonded covalent radii (D8CR) = half of doubly bonded homo atoms Triple bonded covalent radii (TBCR) = half of triply bonded homo atoms : Distance between c~c > distance between c = c > distance between Be > eg > Gea 4 Sens Sooo Ses > Se 2 2 2 ‘SBCR of carbon > DBCR of carbon > TBCR of carbon By default, singly bonded covalent radius (SBCR) is covalent radius, because atoms of non-metals are bonded at least by single covalent bond, while they may or may not form double/triple bonds. 2. Metallic Radius: Half of the internuclear distance between two adjacent atoms of a metal bonded by metallic bond in crystalline lattice structure. Electron Sea Model (Metallic Bond) : In early 1900's, paul Drude came up with “Sea of electrons” metallic bonding theory by modelling metals as mixture of kernels (positive nucleus + inner shell electrons) and outer most shell electrons. ©9 POL QO, O0Q0Q © 0,020.0 o od Kernels. Sea of electrons ‘An array of positively charged kernels is present in a sea of freely moving electron in gaps of these kernels. ‘The negative charge of electron sea helps to bind kernels in the array. Vander waal's Radius : Half of internuclear distance between two adjacent non bonded atoms of an element in a highly compressed state. 29. [=] n covalent bond, electrons are concentrated between the nucleus while electrons in metallic bonds are movable so attraction in covalent bond is more than that of metallic bond, Also, van der waal forces are weakest, so van der waal radius is largest. So, for a particular atom: Covalent radius < Metallic radius «< Vander waal radius For noble gas, only Vander waal radius is calculated. For non metals, covalent radius and Vander waal radius, both can be calculated. for chlorine, Covalent radius of Cl = 4 Vanderwaal radius of Cl = 2 9 for metals, Vander waal radius, covalent radius and metallic radius, all three can be calculated. for lithium : Metallic Radius Lie) — a Vander waal radius Li{g) —+ Covalent radius Element Radius that may be calculated Default radius Metals Metallic, Covalent, Van der waal__| Metallic Non metals Covalent, Van der waal Covalent Noble gases | Van der waal Van der waal Factors affecting Atomic siz @ Nuclear charge (2): When Z increases, attraction on electron increases and thus size decreases (il) Shielding (¢) : When ¢ increases, attraction on electron decreases and thus size increases Effective nuclear charge (2*) : When 2* increases, attraction on electron increases and thus size decreases. (iv) Shell no. (n) : With increase in shell number size increases. () Crystal Lattice = fe > el. |. Body centered cubic Face centered cubic Periodic Variation of atomic size : (i) In s-block and p-block: Along the period: On moving left to right- shell no(n) remains same, but Z* increases therefore atomic size decreases. Since Vander waal radius exists for noble gas, they are largest in their respective periods. it is also explained by excessive shielding caused by fully filled orbitals. eg. : size of elements of 2 period Li> Be> B>C>N>0>FBe>B>C>N>0>F v van der waal Covalent (Z* + size +) radius radius e.g: Order of van der waal radius of element of 2 period order of size Li> Be>B>C>N>0>F Be>B>C>N>O>F Van der waal radius Covalent radius (Z* 7 size +) When nothing is mer default radius. Order of van der waal radius : Li > Be > B >C > N >O > F > Ne > (2* increases, size decreases) When radius of elements is compared on same scale then, 2* is only factor in the period and shell no. n is only factor in group. For period 1, 2, 3 : Size of group 18 > group 1> group 2... H group 18 > group 2... K>Kr Rb > Xe Cs>Rn Fr> Og ned, size of elements is compared on the basis of Exception : Pb > Bi (Expected) Pb < Bi (actual) due to crystal lattice. Along the group : (On moving top to bottom shell no.(n) increases so size increases although the size increases, the rate of increase of size, decreases down the group, due to increase in no. of poor shielding electron. Exception : In group 13 order of size is : Expected: BGacinc TL B y>2 Data based orders: ui Be ui F Na S Me Na cl K ca Br x . Rb sr Rb cs ba Small — Large (i) in d-block: Along the period: ‘On moving left to right size first decreases, then remain constant in middle and than finally increases. & 190 € 160 & & 3 170 % 150 3 3 £ 150 2 vo| 5 3 $130 § 130 8 2 SeTi V CranFe ConicuzA ‘Sei V CrmnFe CoNiCUZA Along the group : 3d ad increase in n dominates increase in z* so size increase: \ 6d { increase in Z* dominates increase. in n so size decreases nt size t ad <4d Pr* > Nd® > Pm > Sm* > Eu > Gd > Th” > Dy* > Ho” > Er > Tm* > yb > Lu 100 lonic Radii (pm) 90 57 59 61 6365 67 69 71 Atomic no. lonic Radius ; It is of two types (1) Cationic radius and (2) Anionic Radius () Cationic Radius: When neutral atom loses electron it forms cation, cation is always smaller than neutral atom. As positive charge on cation increases size of cation decreases. A ——+ A’ —>+ A? + a8 No. of protons = Z z z Zz No. of electrons 2 z4 2-2 2-3 —___—_____5, Z remains same, o ¥,z**, size + (2) Anionic Radius: When neutral atom gains electron ,it forms anion. Anion is always larger than neutral atom. As no, of negative charge on anion increases, size of anion increases. A ——> A —> A? —— + A? No. of protons Z z Zz z No. of electrons Z ZH Z42 243 py Zremains same, o *,2* +, size t (3) Size of isoelectronic species: It is compared by (Z/e) ratio As (2/e) ratio increases ionic radius decreases. eg Na, Mg’, FNAL z> 1 2 9 7 8B e+ 10 10 10 10 10 ze> 1 12 «08 OF 13 Zfe order > Al” > Mg? > Na" > F* > NE onic radius > Al” < Mg < Na" < F< N= Although noble gas are isoelectronic with others, but Z/e can’t be used because of different types of radius, ionic radius for ions and van der waal radius for noble gases. eg: N* > Ne > O*> F > Nat > Mg* > Al* Pi > Ar> S* > Cl > K* > Ca"? > Sc Smallest cation = H* Smallest anion = F* (not H-) Ho Fe ce er r Z 1 9 7 33 53 = 2 0 w 3 Ba Size H> Fre CheBre oF Frect Ber ce > Ne > or > F A =. ’ ES. Se A Sk A Ess s ae PR 7 ie a se > Br Small > Large (Q27_ Which one is tanger van der Waals radius or covalent radius? Sol: van der Waals radius. © Which one is largor crystal radius (metallic radius) and covalent radius? Sol; Metallic radius. © Which of the following has smallest ionic radius. Li, Na’, K’ 2 Sol: * Arrange the following in order of increasi (@) Cl, P*, s*, F° (b) AL", Mg, Ni (©) Na’, Mg*, K°. on Fy (a) F< Cl< St < pe (b) AU < Mg < Nat < F< 0%; (0) Mg < Nat < Kt. Sol Q41 Which of the following has largest and smallest ionic radius : |-,!* and |? Sol: Largest ', Smallest |* 38. (5 Astudent reported the atomic (ionic) radi Sol: Sol: Sol: Q45 Sol: if Cu, Cu” and Cu™ as 96 pm, 122 pm and 72 pm, respectively. Do you agree with the reported values? Justify with reasons. he size of cations is always smaller than its parent atom. Mg°? is smaller than O* in size, though both have same electronic configura- tion. Explain, No doubt Mg’ and ©* both has 10 electrons but Mg” having 12 protons in its nucteus (0 has 8 protons) exerts higher effective nuclear charge and thus shells are more effectively pulled in Mg* resulting to smaller size than O~ | The tonic radii of S** and Te* are 1.84 and 2.21 A respectively, What may be the ionic radius of Se* and p*. 1.842.21 ionic radius of Se* is average of S* and Te* i.e, ————— =2,02A as 16% gp has O, S, Se, Te, P* has ionic radius should be larger than S* because the radii of iso electronics decreases with increase in atomic number. K’ and F” have identical radius about 1.34A. What should be the atomic radi- us of K and F atoms. Atomic radius of K > ionic radius of K* 21348 ‘Atomic radius of F < ionic radius of Fr < 1344 Cations are always smaller than their parent atom; anions are always larger than their parent atom. 39. (Il) lonisation energy and lonisation Enthalpy lonisation Energy: It is the amount of energy required to remove most loosely held electron from isolated gaseous atom/ion to form another isolated gaseous ion. tonisation Enthalpy (OH,): Change in enthalpy when an electron is removed from outermost shell of isolated gaseous atom/ion. A(g) > Ag) + e° (IEor AH, of A) By default all ionization energy [IE] values are specified at zero kelvin (OK) hence at any other temperature, change in energy for ionization process is given by ionization enthalpy (OH,). s. AH, =1E + 2RT He 2 AH, (at zero kelvin) = IE Some important points about IE/OH,,. IE, of A Ie ofA ofA og, @ a(g)—t at @ Eporar > *(g) eee +g) 2+ Ie, of a Gi) A(gyp—E.3*(g) + 3e7 IE = (IE, + IE, + 1E,) of A) (ii) lonisation is always endothermic process (energy is required) for neutral atom or cation. (iv) Successive ionization energy is always increasing IE, < IE, p>d>F. eg: IP, of Be > B > PP of 2s > 2p IP, of Mg > Al > PP of 3s > 3p IP, of Zn > Ga PP of 4s > 4p (v) Extra stable electronic configuration, halffilled (p°, d°, f?) and fully filled (p®, d®, 4) electronic configuration require slightly higher ionization energy. qi) Periodic variations of |E/AH,, Periodic variations of ionization energy (IE), ionization enthalpy (AH,.) and ionization potential (1P) are same. (1) in s-block and p-block: In a period, on moving left to right IE increases (generally) (extra stable electronic configuration like ns? or nsinp? or nsénp* have higher lE than next, element). Example : order of IE, of second period elements: a % Expected: Li < Be << B < GC < N << 0 «< F < 2s' 2s? 2s*2p' 2s2p? 28°2p?_-28*2p" 2s*2p* 2s*2p* Bong) OD Actual: Lic] BeOF>CeNCFO Al> Ga> In > Tl Actual : B > Al < Ga> In < Tl Overall : B > TL> Ga>Al> In Gi) IP, of group 14: C > Si> Ge > Sn < Pb (less exception) C > Si> Ge > Pb > Sn IP, of group 15 :N > P-> As > Sb > Gi (no exception) fiv) IP, of Sn < Pb (v) IP of Cs = Fr (i) IP, of Ba< Ra 42. (2) In d-block: In a period, on moving from left to right 2* increases IE increases (Generally) When an electron is removed from (ns), positive charge appears, hence second (ns) electron jumps to (n-1)d. Ifno. of exchange increases sufficiently, decrement in lE observed. IE, : Se V< Cr < Mn < Fe > Co> Ni Sc V Co>NiMn]Zn 4 + cr(d*) cur(d"") IE, of elements of 3d-series increases form left to right, but IP, of Mn > Fe because of extra stable electronic configuration. IP, ScFel< Co 4d > 5d > Gd 4 Sc >Y>La> Ac IP, of group 10: 5d > 4d > 3d > Pt > Pd > Ni IP, of group 8, 9, 11, 12 : Sd > 3d > 4d > Os > Fe > Ru Ir>Co>Rh Au>Cu>Ag Hg > Zn > Cd 43. Gii) In f-block : © On moving left to right size decreases IE increases (generally), due to increase in nuclear charge (2). “© Give order or IP, or 2 period element? Sol: Be* coon Fro Net 2s! 2p’ 2p? 2p* ape (1) Noble gas configuration + Z* increases IE increases (2) lower shell IP: Be 16 eV/atom : lower oxidation state more stable [lE,, -IE,, ,] < 11 eW/atom : higher oxidation state more stable Example: Al> AU, Al’ > AU] OIE(IE, ~ IE,) = 12.8 eV/atorn > 16 ev/atom > lower OS. stable so Al’ is more stable than Al” 44, AU’ > AL, AL* > AL] AIE(IE, ~ IE.) = 6 eV/atom < 11 eV/atom + higher O.S. stable so Al* is more stable than Al Overall order of stability : AL" > Al’ > Al? (vi) Inert Pair effect In p-block, on moving down the group stability of higher oxidation state decreases and stability of lower oxidation state increases. Because, as we move down the group, no. of poor shielding d and f electrons increases, so attraction on (ns) electron increases which makes (ns)e", inert for bond formation Group 13 Group 14 Group 15 B—-@ | c—+@) n—@® " 2 8 AL si Pp S@ | *S@ | SO] scan “ 2 43 | higher > tower Down the group mal ee as <6 Os. 0s. stability of a Ps s . gee 7 Higher o.s.+ nee Snes Soy, lower o.s.t ® @ @. no Pb o® ae lower > Higher Saag “eg Seas | 05. Os. Order of stability: (i) group 13: Ga! < In” In? > TE Down the group stability of Gi) group 14: Ge"? < Sn’? Sni# > Pb** Gil) Group 15 : As* < Sb" < Bi" As‘*< Sb**> Bi** (iv) Pb* > Pb** Bi'* > Bi® ( Sn < Snv4 45. O¢ Sol: Sol: Q49 Sol: Among the elements Li, K, Ca, S and Kr, which one is expected to have the lowest first ionization enthalpy and which the highest first ionisation en- thalpy? K has lowest first ionisation energy because of larger size. Kr has highest first ionisation energy because of smallest size and ns”, np* configurations. Why does the first ionisation enthalpy increase as we go from left to right across a given period of the Periodic Table? ‘On moving left to right along a period, effective nuclear charge increases. Thus electrons are more tightly held by the nucleus and is therefore their removal is more difficult so the first ionisation enthalpy increases from left to right. Why ionisation enthalpies decrease down the group in the Periodic Table. ‘On moving down a group, valence shells become farther away from the nu- cleus and therefore electrons are less tightly held with nucleus ionisation enthalpy thus decreases down the group. 46. Sol: Sol: The first (IE,) and the second (IE,) ionization enthalpies (kJ mot") of a few nated by Roman numerals are shown below: 1e, 1e, ' 2372 5251 " 520 7300 m 900 1760 v 1680 3380 Which of the above elements is likely to be : (a) a reactive metal, (b) a reactive non-metal, (©) a noble gas, (d) a motal that forms a stable binary halide of the formulae AX, (X = halo- gen). (a) 11 (low IE, and high IE,). (b) IV (high IE, and IE.) (©) | (highest values of IE, and IE, among the given elements), (d) II (moderate values of IE, and IE,). Which of the elements Na, Mg, Si and P would have the greatest difference between the first and second ionization enthalpies. Briefly explain your an- swer. Element which will have stable configuration after removal of one electron will have the maximum difference between IE, and IE, so the element is Na. Na:1s*,2s? 2p®,3s' > Na* :1s?,2s? 2p® > Na® :18?,2s?2p* frome romp A jump in ionisation enthalpy is noticed only when valence shell changes during successive removal of electron. 47. Sol Sol Select in each pair, the one having lower ionisation energy and explain the reason. @)landr, (b) Br and K, (©) Li and Li’, (d) Ba and Sr, (e) Oand s, (f) Be and B, (6) N and 0. (a) Ir (Lower effective nuclear charge). (b) K (Lower effective nuclear charge), (©) Li (Lower effective nuclear charge}, (@) Ba (Larger size of the atom), (©) S (Larger size of the atom), (A) 8 (Ellipticity of subshell), (@) 0 (Nature of configuration) IE, of Be > 1E, of B, Explain why? Removal of electron from Be takes place from 2s whereas in B it occurs from 2p, 2s orbitals are more closer to nucleus and thus more tightly held and removal of electron requires more energy. LE, of O < IE, of N but IE, of 0 > IE, of N. Explain why? Nite?,2522p2 _Ferevltiom2> rs 462 96? 2p? 9 NP 152,26? 2p? aa: P aif tied and this more Te, ees es ses 2p Remevalfrom2p. 0: 157,25? 2p* + 0° : 187,25? 2p® halfiledandtnuamorele, 07 :18?,28? 2p? Na’ has higher value of ionisation energy than Ne, though both have same electronic configuration. Explain. No doubt Na‘ and Ne both has 10 electrons but Na* having 11 protons in its nucleus (Ne has 10 protons) exerts higher effective nuclear charge and thus removal of electron from Na’ requires more energy. 48. || © Why is the second ionisation energy of lithium much greater than that of beryllium? Sol: The electronic configuration of Li* is 1s? and that of Be: is 15?,2s’. It requires much more energy to remove a 1s core electron clase to the nucleus of Li* than a 2s valence electron further from the nucleus of Be* )) Electron Affinity / Electron Gain Enthalpy (H,,): Electron Affinity (EA) : It is the amount of energy released when an electron is added to an isolated gaseous atom or ion. Electron gain Enthalpy (AH,.) : Change in enthalpy when an electron is added to an isolated gaseous atom or ion. By default all electron affinity values are given at zero kelvin (0 K), but at ‘other temperature electron gain enthalpy is given by 5 Ati, = -EA- ght AH (at zero kelvin) = ~ EA Ng) AA _, a-(g) AHA, 424g) Way be sve oF ve always We AH, May be -ve AH, always -ve or +ve for neutral atom for neutral atom Example : in the process, Aig) +e —* 5A (g) If energy released is 20 eV/atom then EA = 20 eV/atom and AH,, = -20 eV/atom A(e) + o —4 5A (g) If energy absorbed is 30 eV/atom then EA = -30 eV/atom and H,,= 30 eV/atom Some important points about EA/AH,, : Aig) AAA 0° (g) a? (8) a ©) ett A(g) + 3e —®4_»A* (g) [EA = (EA 4 EA, + EA,) of A] (iii) Magnitude of successive EA of neutral atom increases 43. [EAI < IEA < EAI < .. (iv) Generally first electron addition of an isolated gaseous atom is an exothermic process. (except for stable electronic configurations) (W) Second Electron addition of an isolated gaseous atom is always ‘endothermic process due to interelectronic repulsion Example: O(g) +e" > 0") AH,,,= ~141 ku/mol (exothermic) O-(@) +e 3 0%(G) AH, = +744 kJ/mol (endothermic) O(@) + 2e" > O-(g) GH, = +603 ku/mol (endothermic) (vi) Formation of polynegative anions (0, N* etc) is always endothermic gg —EALtA aq AD FA preg SAFER p=always ve Relation between Electron affinity and ionization energy : @ Electron affinity of neutral atom = ionization energy of its anion aye Ag) +e" Ae) EA of A= IE, of A- (1) lonisation energy of neutral atom = electron affinity of its cation 1" AB) Ae) te IE, of A= EA of AY 2) lonisation energy of neutral atom is always greater than electron affinity of neutral atom nthe nar ate AY successive IE is always increasing SO IE, of A“ < IE, of A~ EA of A< IE, of A @) EA DHe fe BH. If energy is released tye -ve ave ve If energy is absorbed ~ve +e ve ve 50. Factors affecting electron affinity : @ Effective nuclear charge (2*) increases, attraction decreases, EA decreases Screening constant (6) increases, attraction decreases, EA decreases Shell no. (n) increases, attraction decreases, EA decreases Electron affinity ofelements havingextrastable electronic configuration (half filled and fully filled) is very less or negative. For such elements electron gain enthalpy (AH,,) will be posi e He. EA is negative cals As} stighty | | Kr positive sb xe In these groups EAT down the group Stability of half filled < fully filled (ns? < ns? np*) $0, EA of half filled > fully filed (ns! > ns? np*) eg, NocbeB eg, EA, of Na> All (penetration of ns > np) EA, of K>Ga (vi) Electron density of 2nd period > 3rd pericd elements. So, addition of electrons to 2nd period elements is difficult, hence EA of 2nd period element is less than 3rd period element (in p-block). e] fe] Pelt ALCIAL > [Al cla} cla Al Si P s el eg, EAofOBeccocer Ney EA= Ove EA= @ve an Ne < Be 2p ~r~ Half filled(p*) Fully filled * EA of 3rd period elements : oN O™N Na>ale< si>PeSsec Rot esl. EA= Ove EA= @ve SS Ar< Mg c Al < Na< P< Si< $< cl book ee PPS? enetration —— atts > 2p - Fully filled Half filled(p*) In a group : * EAof group 17: [FeCi]>Br>1 > [eteF]>ar>1 * EAofgroup16: [OSe>Te = S>Se>Te>[0] Mustratio Compare IE of F, F-, Cl, Ct. Solution : () IE ofF>cl =2 Down the group IEY (2) 1EofF>F = Succes higher (3) IE ofCl> ck = Successive IE is higher (a) IE of Fe > Ck = EAof F< Cl From (1) to (4) > IE of F>Cl>Cl > F 52. ass Sol: Electron affinity depends on: (A) Atomic size (8) Nuclear charge (C) Atomic number (D) Atomic size and nuclear charge both . Electron affinity depends on both Top to bottom atomic size Cl, Br, |, and left to right Na O C>N>B (8)B>N>C>D (C)0>C>B>N (0) 0>B>C>D c B,C,N,O Nitrogen electron affinity is negative N attraction? then, electron affinity of sodium is highest Which of then is correct order of ionization energy. (A) Fct le = F< F because successive LE is always increases le = F (aq); AH, =—Heat of hydration : dr reraq + F(@q); AH, +H, +H, Electron affinity of chlorine is more than fluorine. Explain. The orbitals that hold the outermost electrons of the halogens are increas- ingly spread out as we proceed from fluorine to iodine. Due to smallest size of the outermost shell in fluorine, the addition of an extra electron results in strong electron-electron repulsion. As a result, attractive interaction between the incoming electron and nucleus of fluorine atom is considerably counter balanced. This results in low electron affinity for fluorine. (7) Addition of an electron to Na,, is slightly exothermic process, whereas addi- tion of electron to Mg,, is strongly endothermic. Explain. Sol: 9 Méq the two outer shell electrons are paired in 3s orbital. An added elec- tron would need to go into a 3p orbital; it would be effectively shielded from the nucleus. So electron-electran repulsion would dominate over the elec- tron-nuclear attraction In Nat the added electron can pair with the one 3s electron already there. It sees some nuclear charge because it is not completely shielded by the outer most 3s electron, (O71 What is the value of electron affinity of Na’ if IE, of Na = 51 eV Na +Nat, +e IE, = 51 eV Nai, te > Na EA, = -IE, = -51 Which in each pair has higher electron affinity? (@) For ct (8) 0 oro (©) Nav or F (@) For (@ F: EA for Cl is zero (b) 0: : EA, of O > EA of 0 and more positive (© Nar @F: EA, fore =0 (i Etectronegativity : » The tendency of an element to attract shared pair of e- in a covalent bond is called electronegativity. + Itis not a measurable quantity. However, a relative numerical value is given on various scales. s | a—t—8 ENa = ENa, EN, > ENg AEN = 0 AEN +0 Non-polar bond Polar bond * Electronegativity of some elements on Pauling’s scale are : H 2 Li Be B c N Oo F yo i 20 2 a 35 4¢ Na Mg AL Si is s cl oo Ses K Br 08 Practically EN of ; 28 Rb P>H 1 on N>cl * i s>c or Factors affecting electronegativity : @ Nuclear charge (Z) increases, attraction increases, EN increases Gi) Screening constant (a) increases, attraction decreases, EN decreases Gi) Effective nuctear charge (Z*) increases, attraction increases, EN increases Gv) Shell no. (n) increases, attraction decreases, EN increases (¥) Oxidation state increases, attraction increases, EN increases e.g, Fe™ > Fe (wi) %S - character increases, attraction increases, EN increases e.g, EN of sp” hybridised C < sp’ hybridised C < sp hybridised C (wii) EN of surrounding atom increases, EN of central atom increases, @.8,, EN of C in CH, < CH,| < CHCl < CH,F (EN of F > Cl> 1>H) (ili) No. of mare electronegative surrounding atom increases, EN of central atom increases e.g, EN of C in CH, < CH,F < CH,F, < CHF, 57. Calculation of EN of elements : 4) Pauling’s method (on Pauling’s scale) : Based on bond energies = 02085 Een *Bra = 020818 Bond energy of pure covalent bond of A - Ain kcal/mole Bond energy of pure covalent bond of B - B in kcal/mole Bond energy of pure covalent bond of A - B in kcal/mole X, and X, are EN of A and B respectively A= ionic resonance energy. Mulliken’s method (on Mulliken’s scale) IEOFA+EAGtA EN of element & on Mulliken scale = SOA TEACTA x-£ aeA \E and EA are in eV/atom Numerically EN of element on Mulliken scale is larger value than EN of that element on Pauling scale. X, = au EEA poe 56 Where, X, = EN of Aon Pauling scale X, = EN of Aon Mulliken scale Allred-Roschov’s Method (On Pauling’s scale) : x, =0.3502" +0,744 i where, xX, = EN of A on Pauling scale 2* = Effective Nuclear charge = Covalent radius of A (in A) ‘tand = 0.359 Applications of Electronegativity : @ Metallic and Non-metallic nature : Generally metals have low EN and non-metals have high EN. So, non-metallic nature o EN Polarity of bond « EN Covalent Bond te Polar Non-Polar & cloud is unsymmetrically cloud is symmetrically distributed between bonded distributed between bonded atoms atoms cae s st EN, = EN, A——8 AENeO EN, > ENg Non-polar bond SENSO. Polar bond Git) Hanney-Smith equation : % lonic character 16 IX, ~ X, + 3.5 (X - X,)" As (X, ~ X,) increases % ionic character in covalent bond increases If AEN = 21 then ionic character = covalent character If. AEN > 21 then AB is ionic bond If AEN < 21 then AB is covalent iv) Bond Energy AEN As AEN increases, ionic character increases, Bond energy increases (&) Bond length (Shoemaker and Stevenson Equation) : Theoretically : For Heteroatomic molecule 8 A [\ eit tte dag Also, ty # ty # Practically, due to AEN, partial charge generates on atoms and extra attraction is observed. So, observed d,_, < theoretical d,_, ‘Shoemaker and Stevenson Equation dag = Iq thy ~0.09|x, where, d,., = internuclear distance between A and & or bond length of A-8 1, = covalent radius of A r, = covalent radius of B 1 Bond length a 2 (vi) Nomenclature of inorganic compounds : While writing names of covalent compounds, names of atoms with lower EN are written first followed by names of atoms with higher EN eg, :CLO> dichloro-oxide ¥ ‘oxo-dichloride * While writing molecular formula of compound, atoms with lower EN are written on left and atoms with higher EN are written on right e.g. : Oxygen difluoride > F,0* OF, ¥ (vil) Nature of Hydride (H - A) : HA +HO— > H+ xis conjugate oase Stability of conjugate base (Ar) increases, tendency to loose H’ increases, hence, acidic nature of acid (HA) increases. In a group Stability of A o size of A x Acidic nature of HA In a period Stability of A" x EN of A « Acidic nature of HA e6., acidic nature of NH,, H,0, HF NH, —>NH; +H" H,0—> OFF +H" HEF +H" In period, on moving left to right size remains almost same due to same no of shell, but EN of atom increases so, stability of (-)ve charge increases hence acidic nature increases. Stability of NH; < OH” H +r Stability: F ENofB oxidation state of A oxidation state of 8 A-B a 41 A=B -2 +2 ASB -3 +3 a4 e.g, H-Cl ~ EN, ENG oxidation state of H oxidation state of C 2 a i eg, 0=C EN, > EN, oxidation state of © oxidation state of C = 42 42= +4 * For ionic compounds oxidation state = Actual charge e.g, In NaCl, oxidation state of Na = #1, oxidation state of Cl = * Average oxidation state = It is calculated by using formula. Sum of oxidation state of all atoms = net charge (OS. of H = +1) (OS. of 0 = -2) 2 eg. H,PO, > 3+) + () + 4(-2 eg,: H,S,0, = 2(+1) + 2(x) + 5(-2) Absolute OS. = It is calculated by using structure eg,: (bd Nature of oxides (A - 0): Binary compounds of oxygen, in which oxidation state of oxygen is (-2) e.g, Na,O, K,0, MgO, CO,, ZnO are oxides F,0 is not an oxide, as OS. of ‘0 = +2 K,O,, H,0,, BaO, are not oxides, as 0.5. of ‘0’ = -1 NaO,, LiO,, KO, are not oxides, as 0.S. of ‘0" = -1/2 Metallic oxides, generally gives base in water so they are basic oxides. Na,O + H,0 —> NaOH Basic oxide = Non-metallic oxide gives acids in water so they are acidic oxides. ClO + HO —> Hocl Acidic oxide Acid Acidic nature of oxides x EN % Oxidation state of A x Non-metallic nature of A «<———__ metallic nature of A Left to right, EN increases, Basic nature decreases, Acidic nature increases Top to bottom, For s-block, EN decreases, Basic nature increases, Acidic nature decreases, For p-block, EN decreases, Basic nature increases, Acidic nature decreases, For d-block, EN increases, Basic natured Acidic nature increases eg: 62. Basic nature | Acidic nature 1 S02 ClO NOs Ko ciizo Basic nature 4 Acidic nature t Rb20 Ag:0 Basic nature t Basic nature L 6,0 ¥ Acidic nature ! ‘Au0 | Acidic nature t Example: Acidic nature of : ( S0,> 80, O.St Acidic Naturet «on N,O, > N,O, 0.87 Acidic Nature? 6 “a Sb,0, > Sb,0, O.St Acidic Naturet wo (iv) SiO, Se0, > Teo, Non-metallic character? (vi) N,0, >P,0, > Sb,0, Non-metallic character? Q73 Which two elements would you expect to combine in the most violent ions? Sol: sand F : Cs is most electropositive and F is most electronegative. Which is more electronegative in each pair? (a) Ne or F (b) Forel. Sol: @F jr ‘Types of Oxides : @ Acidic oxides : non-metallic oxides are generally acidic oxides which reacts with base to give salt & water. Aqueous solution is acidic. CO, +H,0 —+H,CO, (2H’ + COZ) 8,0, +H,O—+H,BO, (3H" +BO3") 63. @.8. : SOp, P;Og, NzOz, Ng, CO, SIO,, TEO,, SEO, ete. Gil) Basic oxides : metallic oxides are generally basic oxides which react with acids to give salt & water. Aqueous solution is basic. CaO +H,0 —> Ca(OH), (Ca + 20H") e.€. : Na,0, K,0, MgO, CaO, Cu,0. Al,0, etc. Gil) Amphoteric oxides : oxides which react with acid as well as base to give salt and water aqueous solution is basic as well as acidic. ALO, + HO —> Al(OH), AW(OH), +HCL— ACL, +H,0 AW(OH), + NaOH —>Ne[Al(OH),] eg zn |Be | Al Ga sn fcr? [ve [spe [ass | pb Zno | Bea | ato, | Ga,0, | sno | cr,0, | v,0, | Sb,0, | As,0, | PbO nO, PbO, ww) (9) Metal oxides with (0.$ = +4) > Amphoteric (VO, (Basic)] Neutral oxides : oxides neither reacts with acid nor with base. e.g. : CO, NO, NO, Metallic oxides = 41,42,43 Basic except amphoteric +4 Amphoteric except VO, 45,46,47 Acidic except amphoteric Non-metallic oxides + Acidic except CO, NO, N,O (neutral) H,0 (amphoteric) Metalloids > Acidic except amphoteric (As™, Sb™) Nature of Hydroxides (A-O—H) : Xa — Xo S Xo — Xn —> AO™ + Ht (Acidic) A-O-H x Xa—Xo 2 Xo— Xn —» At + OHP (Basic) EN of A decreases, X,-X, increases basic nature of A-O-H increases in NaOH (K, = Xyq = 2.6) 2K, =X, = 14) Therefore, NaOH is basic in nature e.g. : In CIOH 6a. & = Xq = 08) < (% - K, = 1.4) Therefore, ClOH is acidic in nature e.g : Acidic nature of HOF > HOC! > HOBr > HO! down the group EN of halogen decreases, X, - X, increases, Acidic Nature decreases Exception: Acidic nature of H,PO, < H,PO, < H,PO, (Based on resonance) © Which are of the following represent the electronic configuration of the host (8) [Xe]es* (©) [He]2s7 (0) [xe ]2s” Sol: ® In a periodic table from left to right electropositive increases. _. Anatom with high electronegative has: (A) Large size (B) High ionisation pote: (C) Low electro affinity (0) Low ionisation potential Sol: 8 In the periodic table. When we go from left to right the electronegative increases and ionisation potential also increases >> Koeping in view the periodic law and the periodic table suggest which of the | following elements should have the maximum electronegative character? (aye (Bas (c) Bi (0) Sb Sol: a In the periodic table. When we go top to bottom the electronegative character 4 (Decreases) P As i gp | EN The Maximum electronegative Bi character by phosphorus 65. oO The outermost electronic configuration of the most electronegative element. = (A) ns’np? (6) ns? np* (C) ns?np* (D) ns*np* Sol: ¢ In the periodic table left to right electroactivity increases (F) fluorine halogen is the outermost electronic configuration of the most electronegative ele- ment is ns*np® ‘Two elements whose electronegative are 1.2 and 3.0 the bond formed be- tween them would be. (A) tonic (B) Covalent (©) Coordinate (0) Metallic 8 Delta electronegative less than 214 €N<2.1 Electronegative is a measure of the capacity of an atoms to. (A) Attract electrons (8) Attract protons (C) Repel electrons (0) Repel protons Sol: A Electronegative tendency to attract the electron pair. Which of the following is the most electropositive elements. (A) Aluminium (B) Magnesium (©) Phosphorus () Sulphur Sol: 8 ENet EP Electronegativity T increases then electropositive positivity decreases. 5 > Going from fluorine to chlorine, bromine and iodine the electronegativity. - (A) Increases (B) Decreases (C) First decreases then increases (0) Changes randomly Sol: ® Electronegativity decreases down the groups. Lattice Energy: Definition 1 Amount of energy released when one mole crystal lattice is formed from its constituent gaseous ions. A’ (g) +8 (g) + AB(s) (Aly, = eve) Definition 2 : Amount of energy required to break 1 mole of ionic lattice, into its constituent gaseous ions. ‘AB(s)—> A"(g) + 8°() (AH, = Ove) vate Mathematically = Where, a, = charge on cation harge on anion internuclear distance Factors affecting lattice energy (L.E) : OOO) 67. 1) Charge on ions increases, LE decreases LEa(a, x4,) 2) Size of ions increases, LE decreas: Lea (priority of charge > size) (+r) e.g. : order of lattice energy : » 2) 3) 4) 5) 6) Hydration Energy iF > NaF > KF > RDF > CsF (rt Ley NaF > NaCl > NaBr > Nal (rT LEY) NaF < MgF, < ALF, (charge on cation? LE1) HgF, < MgO < Mg.N, (charge on anion? LE*) NaF < MgO < AIN (charge on ionst LET) Mg,N, ALO, ot > Mg < AL gq NY > 0% ro Mg > AL rN > OF (r+) > Mg,N, > ALO, LE > Mg,N, < Al,0, Amount of energy released when one mole gaseous ion is completely dissolved in water. AY (€)—> A'(aq) Bg) > B(aq) Aye OF AY Factors affecting hydration energy : 1) Hydration energy « charge of ions 2) Hydration energy « ——1__ sizeofions Application of HE 1) Size of ion in aqueous medium « HE 2) Mobility of ions in aqueous medium « =z 1 1 3) Electrical conductance «1 ae sizeofion(aq) "HE 4) Solubility « HE AB (5) Ws at faq) + 8 (aa) AME AME Ove Ove i+ B®) An ionic compound is soluble if AH, > AH, eg, For alkali metal ions : Size of gaseous ions : Li* < Na* < K* < Rb* < Cs* Hydration energy (AH,,,) : Lit > Na" > K" > Rb > Cs* Size of hydrated ions : Lit > Na‘ > K* > Rb* > Cs* Mobility of ions (aq) : Li < Na" < K’ ¢ Rb’ < Cs" Electrical conductance : Li" < Na‘ < K* < Rb’ < Cs" Hess’s Law: Energy is a state function and not path function, that is if there are more than one path for a conversion, then energy involved in each path is same. eg: path 3 From Hess's Law : Energy of path 1 = Energy of path 2 £, = IE, +1, From Hess's Law : Energy of path 3 = Energy of path 4 E,=1E, +16, +16, Born Haber's Cycl Born Haber’s cycle is used to calculate Lattice energy. For NaCl (s), Na(s)+ Z cls g) —HH—+ nact() ‘ Jone [pom naw Lig) AH Jowe [ate Nat (g) cl ig) AH = Ay at +L atee Hy e For MgO (s), 1 He Me(s) + 5 02) —SH—> mgows [o0 | parce Mew of AHue Me" (g) 0"? (g) For ALO, (s), 2AL(s) + 2 02@) —H + aos (6) | 20 | Foten 2a 30% AHL [eae enero 2al"(g) 3.0" (e) Valency: ‘Combining capacity of atom Valency with respect ta hydrogen NaH MgH, AlH, SiH, PH, H,S HCL increases decreases” valency with respect to oxygen Na,0 MgO Al,0, SiO, P,Q SO, Cl,0, 1 2 3 4 5 6 7 Based on 0S. a CIH, not possible 7 ClO, possible n. Some important trends- c sommane (2H) 0 Sa — wmpsg «smog Goma eo v3 serene _sendnaso pee sero) = SF? or 97030 ORIEL = ‘Spun jo moumD soon apa ek a ‘peaba ee p40 1 pode Mun LODE ane (pimp mopea ape nee once ap Boag sure PO soem soeaned ‘anor Bunge ome Bump 2830 ‘epee 30 ae aT wont nage noe pass “ae someon, Femme worm mpesoeaory Chapter Summary IMPORTANT FACTS TO REMEMBER 1. Lowest electronegativity 2. Highest electronegativity 3. Highest ionisation potential 4. Lowest ionisation potential 5. Lowest electron affinity 6. Highest electron affinity 7, Least electropositive element 8. Lowest m. pt. metal 9. Highest m. pt. and b. pt. metal 10. Lowest m. pt. and b. pt. nonmetal 11, Notorious element 12, Lightest element 13. Smallest atomic radius 14. Largest atomic size 15. Largest monovalent anionic size 16. Smallest cation 17. Most electropositive element 18. Element with electronegativity after F 19. Group containing maximum no. of gases 20. Liquid element of radioactive nature 21. Volatile d-block elements 22. Element containing no neutron Cs F He cs Noble gases Chlorine F Hg W (Tungsten) He Hydrogen Hydrogen H cs Ke WF Cs Oxygen next to Fluorine Zero group of gaseous elements in periodic table Fr Zn, Cd, Hg, Uub H 73. Chapter Summary IMPORTANT FACTS TO REMEMBER 23. Most abundant element on earth 24. Rarest element on earth 25. Most abundant metal on earth 26. Element having maximum catenation tendency 27. Non metal having highest m. pt., b.pt. 28. Metal showing highest oxidation number 29. Most electrovalent compound 30. Most stable carbonate 31, Strongest alkali (Hydroxide) 32. Strongest basic oxide 33. Best electricity conductor among metals 34. Best electricity conductor among non metals 35. Most poisonous element 36. Liquid non metal 37. Element kept in water 38. Elements kept in kerosene 39. Element sublime on heating 40. Noble metals 41, Amphoteric metal 42. Amphoteric nonmetal 43. Metalloid’s elements 44. Nonmetals having metallic lusture Oxygen at (Astatine) Al Carbon Carbon (Diamond) Os (+8) CsF Cs,co, CsOH Cs,0 Ag graphite Pu (Plutonium) Br Phosphorus 1A group element (except Li) h Au, Pt etc. Be, Zn, Al, Sn, Pb si Si, As, Te, At, Ge, Sb, Po Graphite, lodine 74. Chapter Summary IMPORTANT FACTS TO REMEMBER 45, Heaviest naturally occurring element 46. Poorest conductor of electricity 47, Hardest naturally occurring element 48. Lightest solid metal 49. 90% of Sun mass 50. Amphoteric oxides 51. Neutral oxides of nonmetals 52. Dry bleacher 53. Dry ice 54, Artificial explosive §5. Oldest known organic acid 56. First noble prize of chemistry was given to 57, Some isomorphism substances 58. Some efflorescent substances 59. First man made element 60. Smallest period 61. Largest period in periodic table 62. Largest group in periodic table 63. Most abundant d-block metal Uranium Diamond Diamond Li Hydrogen BeO, ALO, ZnO, PbO,, SnO, SnO, Sb,0,, As,0, etc. NO, CO, H,0, NO ©, (ozone) Solid CO, TNT, ROX — (Research Developed Explosive etc.) CH,COOH Vant Hoff FeSO,7H,0(Green MgSO,7H,O(Epsom Salt), ZnSO,.7H,0 (White Vitriol) Na,CO,10H,0, MgSO,7H,0 etc Te (Technicium) (2 elements) 6" (32 elements) 39/111 B (32 elements) Fe 75. Chapter Summary IMPORTANT FACTS TO REMEMBER 64, Most abundant s-block metal 65. Element having maximum isotopes 66. Highest density (Metals) 67. Highest density (Non Metals) Ca Sn(10) Ir30s Boron Common and IUPAC names of some recently discovered elements Atomic No. | Common names (UPAC names 104 Rutherfordium (Rf)/Kurchatovium (Ku) Unnitquadium (Ung) 105 Dubnium (0b)/Hahnium (Ha) Unnilpentium (Unp) 106 Seaborgium (Se) Unnithexium (Unh) 107 Bohrium (8h) Unnilseptium (Uns) 108 Hassium (Hs) Unniloctium (Uno) 109 Meitnerium (Mt) Unnilennium (Une) Some Subjective Questions - Organize the following in increasing order of the property indicated = radius « Zen Mg < Na’ < 0% < N (N* has greatest Z, Hydrated radii * Small cations due to higher e- density show greater solvation with water mole- cules. So as that size of cation increases as it solvation decreases. Lit > Nat > K* > Rb* > Cs > As the size of central atom increasing as it's acidic nature increasing. SIO, < P,0, < $0, < CLO, : Bcin

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