February 2015 %30 Spectrum Cha eton "istry Me YEE RG, See tis, Concepptea ‘m i You 0 Co a egg Quick Review of Concepts States of Matter p- Block Elements Chemical Bonding P-BLOCK ELEMENTS as Test Series for JEE Main & Advanced JEE Main Test Ride 1 JEE Main Test Ride 2 JEE Advanced Test Ride 1 TEST DRIVE School Practice Ride 1 Board Exam Ride 1 Board Exam Ride 2 Wt t0N |The First Ever Complete Book for JEE Main Giving a Planned Study with Complete Assessment A Complete Success Package for JEE Main 2015 SS CPREPGUIDE Complete Study Material for Physics, Chemistry & Mathematics i More than 10,000 Objective Questions aT) DTN E EXAMINAT eX) ERE RI} ARTS m i Ce 8 cs or 20 Unit Tests & 10 Full Length ey et fart 6) Ve) A th RU ROC RCL aS Sa) TA a Te eles S pees emi al Flea leis PSeriecr EVE ee Cnc asc ,CHEMISTRY | pectrum — Publisher harman Eiiora Head Publishing Manager Coordinator Production Manager Ciro & Aubertsement Geral Manager over € Layout Design Page Designer Diagram pe etng apy tor Prof Reader Head Ofice Phone Fax Email Website Circlation Corporate fie © Publisher PARUTLTAIN YCJAIN SANJAY SHARMA AMITVERNA i SHIVAM TIAL SHISHPAL SINGH ANIL KUMAR GUPTA + S1-s719619948 i angola atiant@gmaom i SHANU MANSOOR SUBODHTKUMAR AMT BANSAL | [BRABAMPAL SINGH [MAYANK, SANDEE® ROW HARISH | SUBODHLANTL | ARANSHA i ARIHANT MEDIA PROMOTERS KALINDI,TP NAGAR, MEERUTE2 o121-2401479,2512970 i o121-2401688 spectum@arianthooks.com | ‘wwrwaribantbooks crn | ARIHANT MEDIA PROMOTERS AS77715, AGARWAL ROAD, ARYA GAN} NEW DELHI? iL 011-47650600 Printed and Published by ara Jain for ' Asihant Media Promoters Printed at rihant Publications (India) Lad i TTP Nagas Meerut (UP) * Allrights reserved. No part of this magazine can be printed in | ‘whe rin pet witost the writen pemusion of he publisher + The tors and publaber of this magesie do heir beta erly the intarnason pblishedbutdo nt ake any respons forthe able accuracy of he ration puslshed + Aspe sujet to Meerut (UP) json oy tase 4 Dear Aspirants, Fist of ll thanks for your appreciation and feedbacks regarding the transformations ‘we did in last issue Your appreciation always motivates us to putin more efforts fr the betterment of spectrum. “Molecules form inthe cool region af space when individual atom or ions happen to collide and make bonding with each other. These are not seen in stars as the bonds ‘would not survive in the high temperatures of stars. Even the electrons of atoms retain their electrons at such huge temperatures. Thus the matter there exists as plasma of ionized atoms and unbound electrons. Over 100 different molecules have been identified by the astronomers in the dense molecular clouds lke Orian Nebula. These molecular clouds ae dense only by astronomical standards even the densest clouds are about 100 billion times lighter and thinner than the earth's atmosphere. Thus, we can say that not even the chemistry around us but the chemistry far away from us is also very complicated and Mysterious Weare trying hard to provide more and more material for your practice within the purview of our limitations. Hope you all will also be trying hard to crack te tough nut called EXAMINATION. The spectrum team will be anxiously waitin for your feedbacks and comments GOOD LUCK oe Contents JEE FINAL LAP, Quick Concept Review @ Class 11th Syllabus (2) TEST RIDER : JEE Main Ride 1 (29) eo al ‘TEST RIDER : JEE Main Ride 2 (82) 1 » ) ‘TEST RIDER : JEE Advanced Ride 1 (85) REVISION THROUGH CONCEPT MAP (40) | REACTION MECHANISMS (12) JEE FINAL LAP e ‘Quick Concept Review @ Class 12th Syllabus (45) JEE ADVANCED CORNER Advanced Stoichiometry PRACTICE SESSION FOR JEE ADVANCED Chemical Bonding and MOT (68) CHEMISTRY PE RUM FOR YOU (70) T DRIVE : SCHOOL PRACT 1E RIDE 1(72) TEST DRIVE: BOARD EXAM RIDE.1 (74) ‘TEST DRIVE : BOARD EXAM RIDE 2 (76) PARTICIPATE AND WIN (79)JEE FINAL LAP QUICK CONCEPT REVIEW Matter exists in the following three different forms based on intermolecular forces of attraction: (i) Solids have definite shape and volume and are rigid due to the strongest intermolecularatomic forces of attraction like covalent, ionic or metallic bonding. (i) Liquids have definite volume, but no definite shape and are non-rigid due to weaker intermolecular forces of attraction like hydrogen bonding or van der Waals’ forces of attraction. {iii) Gases have no definite shape and volume and are non-rigid due to the weakest intermolecular/atomic forces like van der Waals’ forces of attraction. Due to weakest forces of attraction, gases show properties like compressibility and expansibility. They possess kinetic energy and velocity. They exert pressure on the walls of the container in which they are placed and are governed by the gas laws. Plasma and Bose-Einstein Condensate The Fourth and Fifth States of Matter Plasma is considered as the fourth state of matter consisting of highly enargetic and excited particles that ‘exist in ionised form, Plasma is found inside sun and ‘other stars tis also found inside fluorescent bulbs. ‘According to Indian physicist Satyendra Nath Bose and German physicist Albert Einstein, there exists a fifth, state of matter called Bose-Einstein Condensate (BEC). this consists of a dilute gas of Bosons cooled to 2 temperature very close to absolute zero -273.15°Cl ‘Tho donsty ofthis state of mattois about one hundred thousandth the density of normal ai. Gas Laws and Related Terms Name of gas law ‘and definition Formulae 1. Boyle's law Ai ‘constant temperature, the volume ofthe given mass ofa gasis, Vel (Tando constant) B ore =P 1 p22 (F constan’ papas 7 ‘raph yo ot oo 3 x Te inversely proponionalto gpk BM pressure. me a= aaa 2 Charles law At—VecT (andi constand constant pressue, YY lt trevohmeota | PPE AT gwenmassofa TT gasis drectly—(poonstant) = Te proportional to mh fbsolute whore, pT andp ae temperate. presse, voluma, temperature and density of gas respectively, 9 rat 2 FEBRUARY 2015pat (Vand constant) {Av constant volume, tne pressure of 3 given mass of a ‘gasis directly i proportional to absolut tomperature Ba 4, Avogadro's law At Van (T and p constant) ‘constant temperature and pressure, equal volumes of allthe ‘gasos contain ‘equal rumier of molecules, 5. Ideal gas equation ‘gas that obeys all the above staleg lawsis calles an ideal gas and the equation obtained by combining al For mae gas Te abovelovs's fatediceal ges 2M 2M “equation. nt Ti, (combined gas equation) 6. Daltonsiaw ofp, = 0, +P, +, partial pressure ar Fs Wnan nwo or mace =r (Ms +N +A.) i chemically a | nan-roacting gases = 87 q are enclosedina i vessel, the ofessure where, n=, Hs +5 ‘exerted due to the Further, p= xP, ‘gaseous mixtures Eanatpan', ‘he sum of partial 88, Br =%.Pr +205 +205 ‘@oonsenn 3)? pressure oUete where. By Baby ke Prot ach gas. Dati. ond See, Yoke ty 279 prossure, mole Variation of partial pressure and mole traction of each with mole fraction for ideal gas ‘constituent gas in the mature 7 Amagatiawot We =Y+V 4%, partial volume The hora, .V.. total volume ofa Ils mxcure contaiing non-feacting gases are tha parla volumes of diferent ‘gases. Hore patial volume is ‘etined as tne volume ofthe micure is equal to cantruent gas a oral the sum of patil pressure ofthe mixture at volume of each gas. Constant 7 in the modure Values of Universal Gas Constant Rhas different values for different units of pressure(p) and volume (V) and is given by 0 n-t.ate(«29) sma when psi Ni or Visine and in kelvin, (ii) R =0.08205 Latm mol K*, when pis in atm, V isin Land isin kelvin. FEBRUARY 2015 3 PMT FINAL LAP (ii) R=1.99 cal mol" K, when p xV is in calorie and T is in kelvin, (iviIfp, V and T are given in any other units which are not mentioned above then we need to convert them, into any one of the above units and then apply the corresponding R value. It is important to note that, temperature is always taken in kelvin for any value of R Trick to Solve Problems Related to Different Gas Laws For different situation of gases * When T and nate constant, apply Boyle's law. ie. Y= ly + When p andr are constant, apply Charles YM at = Whan Vand mare. constant, apply Gay-lussac’s law, ie, B= Be + Whan and¥ are changing under constant valu ofTanép, apply Avogadro's aw, ie wow am ‘Apply Dalton’ law of partial prossur, requires to find the partial pressure due to a gas na gaseous mixture of non-reacting gases. ‘= Whon all the parameters are changing, aonly combined gas euation, ie ple nth = Ingeneral, gases are collected over water, ite. obtained in moist form, so, thon Pressure of dy gas is caleulated as axon =Pruiegn ~ 2qU0008 tonsion Aqueous tension Qis the pressure exerted by saturated water vapours Volume Coefficient and Pressure Coefficient Charles’ law can also be written as: V=(4273.19K “a where, is temperature in Hatt =0°C, V=Vp, then V, =273.15K very fre te] -moe en 315 fii)PMT FINAL LAP where, a = Cand is called as volume coefficient and is 273.15 defined as the change in volume per degree change in temperature, + For every 1° change in temperature, volume of a gas changes by of V;. Hence, the volume of gas becomes almost zero at 0 K (or -273.15°C). a pen[tesctcs)-n + whe the presse 0 and a=-—! °C" and is called pressure coefficient and is defined as the change in pressure per degree change in temperature. Effusion and Diffusion Effusion is a process by which gas molecules pass through small holes of porous membrane. On the other hand, diffusion is a rrocess by which g ¥ Eoson fo or more IER ee ailfrent gases ye eee intermix When meaner come in contact a =e DBifuson with each other. ey | oeses min The process of effusion and diffusion are shown in the figure below. Graham's Law of Diffusion (or Effusion) ‘The rate of effusion (or diffusion) of non-reacting gases under similar conditions of temperature and pressure are inversely proportional to the square root of their densities or molar masses. + If and f, are the rates of diffusion of two gases of molecular weights M, and M, and densities d, and d,, then 5 Va YM, + IfV, and V, are the volume of two gases diffused (or effused) in timed, and then = Y= andy, = t b o 5M (I m Vs, Va \™, + vo gases ae tse ras) ue diterent pressures and p,, then 4 = pe ten fae “Rae mie + This laws helpful in determining molecular weight and vapour density of diferent gases. 4 FEBRUARY 2015 | SIEGES Kinetic Theory of Gases This theory was developed during nineteenth century to explain ideal gas behaviour in terms of| movement of molecules. This theory is assumptions: based on the following +A. gas consists of extremely small discrete particles called molecules, dispersed through out the container. + The molecules are so small that its volume is neglected in comparison to the total volume of the gas. Hence, the average distance between two gaseous molecules is much large as compared to their size, = The intermolecular forces are Hence, the gas molecules independent of each other. + The gas molecules move in straight Line randomly with high speed. They continuously change direction on collision with each other or with the walls of container. negligible, move freely + The collisions are perfectly elastic resulting no loss of kinetic energy during collision. + The effect of gravity on motion of molecules is negligible in comparison to the effect of collision + The pressure exerted by a gas is due to collision of gas molecules to the walls of container. Higher the number of collisions per unit time per unit area, higher is the pressure. + Ata particular instant different molecules have different speeds, however the average kinetic energy of all molecules is assumed to be directly proportional to absolute temperature, Ey, «7 (Tis in kelvin) + This theory explains macroscopic properties of gases like pressure, temperature, thermal conductivity, viscosity, ete,, and microscopic properties like kinetic energy. + Based on postulates of kinetic theory of gases the following equation can be derived 1 Vv ~L mv, mus where, p= pressure exerted by gas molecules V = volume of the container m= average mass of each molecule N = number of molecules Vig = Fool mean square velocity of gasFormulae Derived from Kinetic Gas Equation Based on the above equation, the following formulae can be derived: (a) Pressure exerted by gas molecules It is given by (0) Average kinetic energy of gas molecules (E,.) For 1 mole of a gas (N =N,), Fug 3 er 3 Ser=3pv 2 2? Sarr 2 For nmole of a gas Ey, SRT 3 3p 3) 3 M2 Fora single molecule Ey. = where, = © 21.3810 J mol” K”, is called Boltzmann constant, Na + Hence, average kinetic energy is proportional to absolute temperature. IfT = 0 K (-273.15°C) Eq=0 Thus, absolute zero (0 K) is the temperature at which there is no molecular motion of gases Degree of Freedom (DoF) + Itis the number of ways a gas molecule can move or store energy. + The total energy of a molecule is equally shared by all its degree of freedom which is called equipartition of energy theorem, + Average kinetic energy of a molecule per degree of freedom is Ler 2 Degree of freedom E cas —__Pestee of freedom _ a ‘¥P® Translational Rotational Vibrational (Ber Molecule) Woncatonie 0 3 Sar ee Diatomic 3 2 0 Ser 2 Pohatome 8 2 we Sar tunes 2 (N-atoms) Povatome <8 ~=~*~«:~S*«NSSSC (Non-linear) + According to kinetic theory of gases, the internal energy of an ideal gas is equal to translational kinetic energy of gas molecule. So, FEBRUARY 2015 5 PMT FINAL LAP Velocities of Gas Molecules ‘Three different types of velocities are defined for gas molecules and are given as (i) Average velocity (7) Ve taccty RF _ RT _ fi sa Elia where, p ~density of gas, M -molar mass of gas i) Root mean square velocity (v...) Gi) Most probable velocity (v,) It is the velocity which maximum number of molecules possess BRT _ flv _ fie VV “Vp VpFive =F BT, Distribution of speed of gaseous molacules also depend ‘on molar mass of gas and temperature, as shown in the curves below. MoM My 19 are (Pr reese | see) 40 amor" MyIN®) 20g mot! 20 aie ao Speed ms") —> Tho For gases with higher molar mas, the average speed is lower andthe distribution of speed is less broad in ‘comparison to gases with lower molar mass, a same ‘temperature, T vale Likewise for same gas, at higher tomporature, tho average speed is higher and te cistribution of speed is more broad in comparison to gas at lower temperature, FEBRUARY 2015 Collision Properties ‘An effective molecular collision is important during a chemical reaction between gases. Also, transport properties of gases like diffusion, effusion, ete., depend on molecular collision. ‘The following properties are related to molecular collision: (i) Collision cross-section {6} In the figure shown below, for a successful collision of approaching molecules with molecule A, they should approach within a distance of one diameter (d = 2r) of A. Hence, the area of target to collide molecule A is the circulararea, rd, and this area is called colision cross-section. [he carte othe mobile 8) camos in dot cont ‘of molecule A soe Wo ‘molecules colds.) > a The target represented for wo band melecales ‘ecole isa circle sporosch A, wth diameter ut enly ‘Area = (27 = na Bi calle - ~The cant athe molecu ‘ater away tan ds tore Collision frequency (z) It is the number of collisions that a molecule undergoes in a second. It depends on pressure (ie. number of gas molecules per unit volume) and distance travelled by the molecule. From kinetic theory of gases, 5 Pp BN, vyox{2 Nave () (iii) Mean free path (2) Tt is the average distance travelled by a molecule between two successive collisions. distance travelled in one second «ay ~ Gumber of collisions in one second ~ Z Hence, =" orpa 2, TEN,op "** axp ‘This implies 4 is directly proportional to temperature and inversely proportional to pressure and collision cross-section {size of molecule) DEALS, OFFERS & MORE... Shop at arihantbooks.com CASH ON DELIVERY (COD) FACILITY AVAILABLE NOW Sie [coerce tere ErSoerecketeind tad caedesedeneReal Gases A Deviation from Ideal Behaviour ‘The gases which obey gas laws are called ideal gases, and those which do not obey exactly are called real gases. + Real gases show ideal behaviour, ic. obey gas equation under moderate conditions of temperature and pressure (especially when pressure tends to zero). + However at high pressure and low temperature real gases show major deviation from ideal gas behaviour, Reasons for Deviation from Ideal Behaviour It is mainly due to the following assumptions of kinetic theory of gases which do not hold good under all conditions ( Intermolecular forces of attraction between two gas molecules is negligible. {il) Volume occupied by gas molecule is negligible in ‘comparison to the total volume of gas. Compressibility Factor (Z) : An Explanation to the Deviation from Ideal Behaviour ‘The deviation from ideal behaviour can be explained on. the basis of compressibility factor (Z), which is defined as the ratio of measured molar volume (V,) of a gas to the RT. molar volume of an ideal gas {vz =*"), at same 5 ( >| temperature and pressure, ie, Z= Y= =—Va_ = ‘The following three values of Z are possible i) When V,=Vg, Z=1 and the gas behave as ideal (perfect) gas. At very low pressure and high temperature real gases behave as ideal gas. (ii) When V,, > V°,, Z > 1, Le. the gas is less compressible than expected from ideal behaviour and shows positive deviation. This happens at high pressure, pV, > RT (iii) When V,, < Vg, Z°<1, ic. the gas is more compressible than expected from ideal behaviour and shows negative deviation. This usually happens at intermediate pressure, pV, < RT. _PVn P Remember 2-2 =e VM ‘where, M = Molar mass of gas. + The variation of Z with pressure for different gases is shown by the graph below: PMT FINAL LAP C7 aogl oat 250 abo @b0_ abo 100 iba van der Waals’ Equa’ + In order to rectify the errors caused by ignoring the intermolecular forces of attraction and volume of gas molecules, a correction in pressure and volume terms in ideal gas equation was necessary. + Johannes van der Waals’ proposed the following modified equation which is valid for real gases up to a large range of temperature and pressure. isl pressure (o) toal vonane nRT | Measured volume ) Volume comection conse molecu volume [Weasired Pressure comes factor to conse Invomovecutar for ‘+ There is a positive sign to pressure correction, because when intermolecular force is considered, the molecule ‘will exert less pressure to the wall, Hence, measured pressure will be less than the pressure predicted by ideal gas equation. + There is a negative sign to volume correction, because when molecular volume is considered, the volume in which molecules can move becomes less than the total volume of container. + Here a and b are van der Waals’ constants, where a is an indirect measure of magnitude of attractive forces between molecules. Higher the value of a, higher is the ease of liquefaction of the gas. Hence, higher the value of, higher is the strength of van der Waals' force. Unit of a atm? mol” or Nm’ mol” or Jm'mol” + b is a measure of the portion of the gas which is not compressible. Unit of b: L mot”! or m’ mol" FEBRUARY 2015 | RIESGO 7PMT FINAL LAP Boyle Temperature (7,) Itis the temperature at which real gases obey ideal gas equation over a wide range of pressure and is given by “Rb Hence, pV “constant or Lim| 224) 0 ual + As T, xa, higher the ease of liquefication higher, is the value of 7, van der Waals’ Equation at Different Conditions (a) At low pressure V >> b, hence van der Waals’ equation (for 1 mole of gas) becomes Rr Ver) Atextremes low pressure V >> a, b, hence Cc both the terms and b can be neglected v Hence, van der Waals’ equation becomes pV =RT (For 1 mole of gas), Le. real gas behaves as an ideal gas. (c At high pressure p >> %, hence 4 can igh P Perea v be neglected, and van der Waals’ equation becomes PIV ~b) = RT (For n=1mole) oraz a14 Be RT RT (a) At ow temperature Both p and V are small. and hence both pressure and volume corrections, are appreciable, Hence, there is no change in the van der Waals’ equation, Limitations of van der Waals’ Equation + Although it is able to explain behaviour of real gases over a wide range of pressure and temperature, it yet shows considerable deviation at extreme low temperature and pressure, + Values of a and b do not remain constant over the entire range of temperature and pressure. Liquefaction of Gases + gas can be liquefied by decreasing temperature and increasing pressure. + The following critical states are defined for liquefaction of gases: () Critical temperature (7,) It is the minimum temperature above which the gas cannot be liquefied, ever a large pressure is applied. It is given by, 8a <27Rb + Gases having higher intermolecular forces like NH,,H,0, SO, CO,, Cl, ete, have higher value of 7, and can be easily liquefied However, gases having very low intermolecular forces like H,, He, N, , Ar, O,, etc,, have lower value of T, and are very difficult to liquefy, (3) Critical pressure (p,) It is the minimum pressure required to liquefy a gas at its critical temperature and is given by @ ne (ii Critical volume (V, Itis the volume occupied by a mole of gas at critical temperature and pressure and is given by P= V, =3b Remember Critical compressibility factor (Z,) is given by z, = PM: 30.375 RT, 8 All gases behave as van der Waals' gas if its critical compressibility factor is equal to 0.375 Liquefaction of CO, gas Thomas Andrew studied the isotherm of CO, and obtained the following graph showing’, p, and V, for CO, + From this graph it is clear that the T, and p, Vanestorco, ares ff and 73.8 bar p respectively. . + At 50°C and above, the 2 isotherm of CO, looks © like that of an ideal gas. & However at any temperature below T., the graph has 3 parts, + In the first part from A to B, volume decreases on increasing pressure. In the second part from B to C, volume decreases suddenly at constant pressure indicating liquefaction of gas and from C to D there is an appreciable change in pressure for very small change in volume, Isotherm of CO, showing erica temperature FEBRUARY 2015 | (iturin eeeLiquid State Intermolecular force in liquids is intermediate of gases and solids, which is stronger than gases and weaker than solids, + They are held together by van der Waals’ forces like dipole-dipole attraction, London forces, hydrogen bonding, ete. + They have definite volume, but not shape as the intermolecular forces are not enough to fix the molecules at a definite position in crystal lattice. + The densities of liquids are intermediate of gases and solids and decrease with increase in temperature, Other Physical Properties In addition to above mentioned liquids possess the following physical properties: (a) Evaporation When kinetic energy of a liquid molecule exceeds intermolecular forces of attraction, it escapes as vapour and the process is called evaporation, The kinetic energy and temperature ‘onus of rest ofthe liquid evaporation due to loss of energetic Kinetic energy cistrbution in iquids molecules. Water is kept cool inside earthen pot is based on this principle, Evaporation takes place at any temperature below the boiling point of a liquid and its rate increases with increase in temperature due to increase in kinetic energy of molecules, and can be explained by the above graph. Vapour pressure During evaporation or boiling, the pressure exerted by vapours in equilibrium with liquid at a particular temperature is called vapour pressure. CG The pressure due to vapours ata given temperature Tis jven by p= RT =CRT given by p= = where, C is concentration of vapours. ‘Vapour pressure increases with rise in temperature and can be calculated by Clausius-Clapeyron equation as; AH, (1 1) tog (22) ~ Ao (4-1), »7, la)" aa0aR 7) 7 where, AH,,, is molar enthalpy of vaporisation, + Vapour pressure due to intramolecular hydrogen bonding in a molecule and decreases due to intermolecular hydrogen bonding between molecules, PMT FINAL LAP (c} Boiling point The temperature at which the vapour pressure of a liquid becomes equal to the external (atmospheric) pressure is called boiling temperature at that pressure. If the external pressure is 1 atm, the boiling temperature is called normal boiling point and it the external pressure is 1 bar, the boiling temperature is called standard boiling point. Heat of vaporisation (AM,,.) Its the heat required to vaporise a unit mass of a given liquid at constant temperature, It depends on intermolecular forces and temperature AH, decreases with increase in temperature and becomes zero at critical temperature. Surface Tension and Surface Energy ‘The force acting along the surface of a liquid at right angle to any line per unit length in called surface tension. @ + Due to surface tension the molecules at surface tend to acquire minimum surface area. + To increase surface area, the given force must overcome surface tension, Hence, the energy required to increase surface area by one unit is called surface energy Surface tension (r) = Wor Change in area Force Length Unit =Nm“ + Due to surface tension, liquids tend to rise or fall in IT cos 8 1g p= density of liquid 6 = angle of contact. capillary tube, and is given by h= where, 1 =surface tension, 1 = radius of capillary, Viscosity and Fluidity + Viscosity is the measure of the resistance offered to the flow of liquid due to intemal friction between two liquid layers. + The viscus force between two liquid layers of area of cross-section A, separated by a distance dx having velocity difference dy is av Pena 1 & where, nis coofficient of viscosity, and is constant for a liquid ata given temperature Unit of n {CGS Unit) + Viscosity decreases with increase in temperature and E 7.303 RT + The reciprocal of viscosity is called fluidity. FEBRUARY 2015| QI RSGn 9 Nem or Pa-s (SI unit), poise or g cnv's" can be calculated as logy, 1 =10gy. AJEE FINAL LAP p-Block Elements Group 13 Elements (The Boron Family) + Boron family contains boron, aluminium, gallium, indium and thallium with general valence electronic configuration of ns?, np + Boron is a non-metal with high melting and boiling point due to formation of strong crystal latice. Rest of the elements are soft metals with low melting point and high electrical conductivity. + Physical properties like atomic radius, ionisation enthalpy, electronegativity and melting point do not follow a reqular trend down the group, as shown in the table below: Propery ———reaulartv in peason ‘Alomicradus Ga < Al Poor screaning effect of dteectron of Ga tonisation —-«sB> T1>Ga> Poor screening atlect of 3 enthaloy Al> in and electrons, which are unable to compensate increase in nuclear charges. Electronegatvity B > TI> In> — Irregulary in atomic radius, Ga> Al Meting pont 8 > Al>Tl> Formation of strong crystal In> Ga lattice in boron. ‘+ Ga has the second lowest melting point (29.8°C) after Hg, but having very high boiling point of 240.3°C. Hence, it can remain in liquid phase at a larger range of temperature and is used to temperature. measure high = Gallium is very useful in semiconductor electronics in form of gallium arsenide (GaAs), which converts light directly into electricity = GaAsis covalent erystal with zincblonde crystal structure, with Ga in-+ 3 oxidation state ' eis propared by the following reactions, 2Ga+2AsCl, —> 2GaAs+3C1, GalCH,}, + ASH, —> GaAs + 3CH, ' Iehas many advantages over silicon a8 a semiconductor and is Used in the manufacture of devices such as laser diodes, solar cells, infrared LED, optical windows, ec. = The advantages are, it has higher electron mobility, more resistant to heat and produces less noise in comparison to silicon diodes. 10 FEBRUARY 2015 | Git ease) Chemical Properties (i) Oxidation state and bond type + Band Al show +3 oxidation state (OS) and Ga, In, TL show both +3 and +1 oxidation states. + The stability of +3 oxidation state decreases and +1 oxidation state increases down the group. Ga** > In** > TI*, Ga* 2MNis) where, M= group 13 element. TL also forms T1,0 with O, REMEMBER ' Although Alis more reactive than, itis stable in air and water de to formation of Al,0, oxide layer that prevents its further oxidation (reaction). ' Acidic nature of oxides decreases down the group. 3,0, >AL,0, >Ga,0, >In,0; >110, ‘Acidic “pmphoteic Bose ‘Amphoe Bate (ii) Reaction with acid and alkal + B doesn’t react with acids and alkali even at moderate temperature, but when fused with alkali, it liberates Fi, 2B + 6NaOH—> 2Na,BO, + 3H, + Both Al and Ga react with mineral acids and aqueous alkali showing amphoteric nature. 2Al(s}+ BH,0° (aqh+6H,0()— fovith did) 2{AM(H,0),}"* (aa) Hexaaquaaluminium (11) ion +3HL (9) 2Al(s) + 20H"(aq) +6H,0() —> 2[Al(OH),| (ag) +3H, () (ith etka ‘Tetrahydroxy aluminate (111) ion + Inand TI react with dilute acid liberating H, gas.(iv) Reaction with halogen = They form trihalides. All trihalides of group 13 elements are known except TI, + The fluorides of Al, Ga, In and Tl are ionic, whereas the rest are covalent in anhydrous form, REMEMBER = Anhydrous AICI, is covalent, but wihen hydrolysed it gives AP*+ Ag ions showing ionic character. Cl, +6H,0—> (ANH,0} |" +3C1~ (vite Hello += This solution conducts electricity and also acidic innature, ast ives 1” ion [ANH,O161"* (ag) — TAIIH,O}, (OHI + HY + The halides form complexes and the ability to form complexes decreases down the group. B only forms complexes of the type BX,L, whereas others form complexes of type MX,I, due to the presence of vacant d-orbitals. Here M= Al, Ga, In, Tl ‘+ All trihalides are Lewis acids and the electron accepting tendency decreases on moving down the group. + For different halides, the acidic strength follows the order BF, < BCl, < By This is due to back bonding in case of BR, (v) Formation of oxyacids Among group 13 elements, only B forms oxyacids when B,O, reacts with water. The structure of some important oxyacids are given below. iN b " | » 8 | oo {N74 o BM f Loo” I | 4 COthoboric acid H,0,) Metabo acid [1H50,4n] Anomalous Behaviour of Boron Due to small size, high electronegativity and non-availability of d-orbitals, it shows the following anomalous properties: (i) It is a non-metal with very high boiling point, ‘whereas others are metals with low boiling point. (ii) It forms only covalent compounds, whereas others form both covalent and ionic compounds. (iii) Its maximum covalency is 4, while that of others are 6 due to the presence of vacant d-orbitals, (iv) Only boron exhibits allotropy and also exists as both crystalline and amorphous forms. JEE FINAL LAP (v) Its oxides and hydroxides are acidic in nature. Its hydrides are more stable in comparison to others. (wi) It shows diagonal relationship with Si, due to its small size and similar e/m ratio, Compounds of Group 13 (a) Diborane (B,H, ) Diborane is a colourless toxic gas thal catches fire on exposure to air releasing enormous amount of energy. BH, +30, —+ B,O, + 3H,0; AM = ~ 1976 kJ mot + Itis prepared in the following manners: ABR, +3LiAlH, —S2"22° 598,14, +3LiF +348, 2NaBH, +1, 9" 5 BH, +2Nal+H, 2BCl, +6H, 2 BH, + 6HCL + shows the following chemical properties BH, +6H,O—> 2H,BO, + 6H, (@) B,H, +2KOH +2H,0—» 2KBO, +6H, (9) 2B,H, +2Na =“ NaBH, +NaB,Hy ByH, +X;—9 BiH, X+HX BiH, +2CO—> 2BH1,CO BH, + HCI B,H,Cl+H, @) BH, -+2NH, — 5 8,H, 2NH, BH, -2NH, is ionic and exists as [BH, (NH,),)'IBH,I- which on further heating in excess of NH, forms boron nitride. However on heating at 200°C, a volatile compound borazole or inorganie benzene is formed. 3B,H, -2NH, —> 28,NH,+12H, Banana Bonding 2 Hg shows banana bonding, whore the tarminl B—H bonds aro guar two centred-two electron bonds (2c-2e) whereas the bridged bonds {8—H—8} are three centred-two electron (3c—2e} bonds, as shown below Bio rarogen Teeinal hereon “BW Shans stBpHe NAN 17 ‘Banana ond (b) Borax It is a crystalline solid and exists in three forms such as prismatic borax (Na,B,0;-10H,0), octahedral borax (Na,B,0, -SH,O) and borax glass (Na,B,0,). BRUARY 2015|@itmia eases 17JEE FINAL LAP + Borax exist as [B,O, (OH), P” ions as shown below. ft 0 ho—B: ‘O ON Lo af I OF Structure of [8 ,0(OH),J* a—oH Some of the important chemical reactions are Na,B,0, +7H,O—> 2NaOH + 4H,BO, Na,B,O, + 2HCI + 5H,O—» 2NaCl + 4H,BO, Borax when heated strongly forms a transparent glassy mass, called borax bead, which is used in qualitative analysis for the detection of coloured radicals like Ni**, Co**, Cr", Cu’, ete, (Borax bead test) 1NojB,0, 10H,0—*—y NaB,O, 1 2nano, +B:0, (Gorax bead) C00 +B,0, —* > Co(BO,), (Blue) C0, +38,0, 4 + 2Cr1B0,), (Green) (0) Orthoboric Acid (H,80.) It is propared from borax as Na,B,O; +2HCI+5H,0—+ 2NaCl+4H,BO, It is a weak monobasic Lewis acid Itacts as a Lewis acid by accepting electron from OH ion as shown below B(OH), + 2HOH—» [B(OH),|” + H,0* It is sparingly soluble in water, but highly soluble in hot water, It shows the following reactions on heating Red hot 11,80, 5 1180, —*+H,,0, 2282 55,0, Ithas a layer structure in which planar BO, units are joined through hydrogen bonds. ane trigonal planar (0H), cnt 12. FEBRUARY 2015 | [ity Arai (d) Aluminium Chloride (AICI;) + IL is white in pure form and acts as a strong Lewis acid. Itis extremely hygroscopic and fumes in moist air due to formation of HCL vit monomer above 800°C with spthybridisation (triangular planar), however below 400°C, it forms dimer (Al,C,) with sp” hybridisation (covalent and 1 coordinate bond) as shown below: es cy &, a Se Ae ee Ko a Na + Some of important reactions of AICI, are AL,Cl,.12H,0—24 Al,0, + 6HCI+9H1,0 AL,Cl, +12NH, —> 2(AICl, -6NH) Group 14 Elements (Carbon Family) + C(6),$i(14), Ge(32), Sn (50) and Pb(62) belong to this group with general valence electronic configuration of nst, np? + Cand Si are non-metals, Ge is @ metalloid, whereas Sn and Pb are metals. exists as + Physical properties follow regular trend except ionisation enthalpy, density, electronegativity, melting point and boiling point. REMEMBER The first ionisation energy decreases regularly up ta Sn and thon inereasos from Sn to Pb duo ta poor shialding of d and orbital electron, whereas second, third and fourth ionisation enthalpy follow iregular trend, "= Molting point decreasos from C to $n and then ineroasos from ‘Sn to Pb, whereas boiling point regularly decreases down the ‘group. This is because the metalic Sn and ?b donot use alt four valence electrans in metalic bod formation = Density decreases from C to Si and then normally increases from Sito P. Other Properties Catenation Carbon shows maximum catenation (ability to form chain and ring structures) due to high C—C bond enthalpy and this tendency decreases down the group due to decreases in bond enthalpy.