PRINCIPLES RELATED TO PRACTICAL CHEMISTRY For NEET-UG (MEDIUM : ENGLISH) ALLENChemist’ sieretuiod to Prac che a] ih ALI a Pre Medical Physical chemistry | 01. | Volumetric analysis 7 02. _| Enthalpy of solution of CuSO, 8 03. __| Enthaipy of neutralization of strong acid and strong base 10 04. _| Preparation of lyophilic and lyophobic sols 12 (05, _| Kinetic study of the reaction of iodide ions with hydrogen peroxide at room temperature 16 06. _| EXERCISE : Multiple choice questions 7 Inorganic chemistry 01. | Sattanalysis 2 (02__| Preparation of inorganic compound 37 (03, | EXERCISE : Multiple choice questions 39 ‘Organic chemistry 01. _ | Determination of extra elements 45 (02. _| Detection of functional groups 48 : 03. | preparation of organic compounds 56 | 04. | EXERCISE : Multiple choice questions 60 NEET SYLLABUS PHYSICAL CHEMISTRY : The chemistry involved in the titrimetric exercises - Acids, bases and use of indicators, ‘onal acid vs KMnO,, Mohr's salt vs KMnO, Chemistry principles involved inthe following experiments : Enthalpy of solution of CuSO, Enthalpy of neutralization of strong acid and strong base Preparation of tyophilic and lyophobic sols |. _ Kinetic study ofthe reaction of lodide ions with hydrogen peroxide at room temperature INORGANIC CHEMISTRY : © Chemical principles involved in the qualitative sat analysis: Cations : NH; , Pb", Cu’*, Al*, Fe”, Zn”, Ni", Ca”, Ba”, Mg" Anions : CO? ,S*, NO, , Cl’, Br, I, NOs", SO3 (Insoluble salts excluded) © The chemistry involved in the preparation of the following Inorganic compounds : Mohr’s salt, potash alum ORGANIC CHEMISTRY : © Determination of extra elements (Nitrogen, sulphur, halogens) In organic compounds; Detection of the following functional groups; hydroxyl (alcoholic and phenolic), carbany! (aldehyde and ketones) carboxyl and amino groups Im organic compounds. © The chemistry involved inthe preparation of the following ‘Organic compounds : Acetanilide, p-nitro acetanilide, aniline yellow, ladoform. oe |All rights including trademark and copyrights and right of translation etc reserved and vested exclusively with Allen Career Institute Private Limited. 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All reasonable care and diligence have been taken while editing and printing this publication. Allen Career Institute Private Limited shall not hold any responsibility for any error that may have inadvertently crept in, Allen Career Institute Private Limited is not responsible for the consequences of any action taken on the basis ofthis publication,Chemisty : Physical Chemistry PHYSICAL CHEMISTRY | QUANTITATIVE ANALYSIS (VOLUMETRIC ANALYSIS) | + Vatmee ana the process by uch the aunty ofa etance pes inthe sen scion i determined by reacting it with soliton of other substances of known concentration given volume of the solution of unknown concentration is treated with the soltion of the other substances of known concentration then by comparing the equvalence af the two soon, concentration ofthe unknown soliton can be determined. The process is known as Titration. + In shor tration may be defined asthe process by which concentration of uniown soliton i determined with the help of a solution of known concentration ‘Some Other Terms used in Volumetric Analyst 1. Standard Solution : A sohition of known concentration is called a standard solution, concentration of | solution is generally expressd in terms of normality (N) or molarity (M) 2, Primary standard : The substances whose standard sohtion can be prepared directly by weighing scaled ‘Primary standard eg. oxalic ack, ferrous ammonium sulphate AA primary standard isa compound of suficent purty in uhich total amount of impurities does not exceed 0.01-0.02% “The substance to be used asa primary standard shoud also say the following requirements: 1. Ttmust be asl aval in pre and ry form 2. Ie should not undergo change in air i.e. it should not be hygroscopl, oxidised by ar or affected by gases such as carbon dioxide present in the atmosphere or lose water of cystallzation, so that it can be stored safely ak job en tae dette pe yor a Be cine casa rs cobra ce ah wa & Its reaction with another substance should be instantaneous and stoichiometric. ay te iienias tian amauta =o on acral iw at pans ear: Hoo, im sg ‘carbonate, sodium tetraborate, potassium hydrogenphthalate, oxalic acid, ferrous ammonium sulphate =n irgearobciyvcapt eneia teye eto ie ciwtenaa eee eesae ae, ‘Sodium carbonate has characteristics nearer to the primary standards therefore its standard solution can be aA tony cect weary ak ect ct 16004 of aden cnt ecb dated pS of ad ina the solution (Molar mass of sodium carbonate is 106 g mot”). Oe SE a aia ctne Sin gsm mut ecie!i cae eee ca peaks GARE Indra wand mmr ok a a ne Te aecem etn wg Ena ca atte roped Wy ee wae soo ‘A solution of secondary standard is the one which may be used for standardization after finding out its exact Re sr toes anker tase paste pana cal = a eS aa james el ey ng a + Before starting titrimetric analysis, you should be familar with some techniques such as, weighing by using chemical balance, preparing standard sotion, measuring woke by using burtte and pipetteChemistry : Physical Chemistry "Normality (N) Normality of a soliton is defined asthe number of gramrequivalents of solute present per litre of solution. [Number of gram — equivalents of solute ‘Volume of solution (in litres) 1y_Mass of solute ingrams perlite of solution Equivalent mass of the solute Wha E “Viaie) W = Mass of solute in gram, E = Gram-equivalent mass of sohute Vieq = Volume of solution in litre. ‘Titrant : The solution which is generally taken in burett is called titrant. Titer : The solution which is generally taken in conical flask with the help of pipette is called titer. Equivalence Point: The point at which the titrant and titer react completely Is called the equivalence point. End Point : The point at which the solution used in titration react completely and is indicated by the Indicator by changing its colour, is called the end point. “There isa difference of 1 drop in equivalence point and the end point. Indicator : The chemical substances which when added to titer during titration indicate the completion of the reaction by changing its colour atthe end point ae called indicators, ‘Types of Indicators : Depending upon the nature of the solution used in titration, indicators are divided {nto four types (@) Internal Indicator : The indicators which are added to the titer during titration are called internal indicators eg, Meth orange, phonclpthalin et. Methyl orange : Methyl orange isa weak base and is yellow in colour in the unionised form. “The anion formed from the indicator isan active species, which on accepting a proton (Le acting as Bronsted Lowry base) changes from the benzenoid form to the quinonoid form. The quinonoid form fs deeper in colour and thus is responibe forthe colour change atthe end point. Benzenoid form of the anion Quinonoid form of the anion (Yellow in colour (Pinkish red in colou Phenotphthalein : Phenoiphthalain is @ weak acd, therefore It does not disociate In the acidic tedium and remains in the unionsed form, which is colourless. Normality HP —> H'+Ph” Unionised lonised Colourless Pink In the acidic medium, equilrium les to the left. In the allaline medium, the lonisation of phenolphthalein increases considerably due to the constant removal of H’ lons released from HPh by the OH" fons from the alll So the concentration of Ph jon increases in the solution, which imparts pink colour to the solution, HPL HY + Pr NaOH = —> Na’ + OFF H+0H —> HO For a weak acid vs strong alkali tration, phenolphthalein is the most suitable indicator. This fs 20 because the last drop of added alkall brings the pH of the solution in the range in which phenolphthalein shows sharp colour changevty Chemistry : Physical Chemistry ALI = Fre Meal alence intemal cling as id form 2 acidic ation of | HPh by imparts hs i 50 + which comes 6 tenes cermin secon aE ‘Choice of Indicator : In the titration of strong acid and a weak base, methyl orange is chosen as Indicator. When titration between strong base and weak acd is to be performed then phenolphithalein 's a good indicator. in this case alkalis dropped from the burete and acid is taken in the titration flask. Colour of the solution taken in the titration flask changes from colourless to pink, This change of colour is easily perceptible to the human eye, If we take alkali in the titration flask, the colour change will be from pink to colourless and accuracy in noting the colour change may be less. Inthe ttration of strong acid versus strong base anyone of the above indicators can be used. For the titration ‘of weak acid vs weak base no indicator is available (b) External Indicators : These indicators are not added to the titer they are used outside to determine the end point. External indicator is placed on a white tle in the form of small drops Dring the titration, a glass rod is dipped in the flask and then i s touched to the drop of indicator placed on the tile. At the end point the colour of indicator changes onthe tie. For example Potassium ferrocyanie is used as extemal indicator inthe titration of K,Cr,O, and ferrous ammonium sulphate (©) Self Indicator : If one of the solution used for titration changes its colour atthe end point then that solution is called self indicator For example in the titration of KMnO, & ferrous ammonium sulphate ‘or KMnO, and oxalic acl, KMnO, solution acts as self indicator, It tums the solution from colourless 10 pink atthe end point. (@) Adsorption Indicator: This type of indator are used in precipitation titration, This indicator gets ‘adsorb on the surface of the ppt formed and changes its colour at the end point. In the titration of ‘AGNO, and NaC, fuoroscene is used as indicator. ‘Types of Titrations : On the basis ofthe nature of chemical reaction, trations are of four types @ Acid-Base .Titrations @Oxidation-Rediuction Tirations (Redox titration) (G) Precipitation Tirations (@) —Complexometrc trations. In the prescribed sylabus acid base and oxiation-reducton titrations are included In oxidation reduction titration one of the solution is of an oxidising agent and the others of a reducing agent. For example - tration of potasslum permanganate (KMnO,) soliton with oxalic acid or with ferrous sulphate solutions or with ferrous ammonium sulphate. ‘Theoritical Aspect of Volumetric Analysis Volumetric analysis is based on the law of equivalence. When two substances react together in solution, they always do so in the ratio oftheir equivalent masses. ‘That Is one equivalent of an acid react completely with one equivalent ofa base, Similarly one equivalent of ‘an oxidising agent oxidises completely one equivalent a reducing agent. ‘On the same bases the Normality Equation has been derived, Le NV=NV, NN, and V, are the normality and volume of one solution, N, other saluton 1nd V, are the normality and volume of the‘Chemistry: Physical Chemistry Ina single titration : If one of ccan be calculated. {t molarity of the solutions is glven then the equivalent equation i changed in terms of morality as follows (First write down the balance equation of the reaction, (i) Note down the stoichiometric coefficients of the reacting solutions (ii) Suppose the balanced equation of the reaction is - aA + BB— Product a and b are the stoichiometric coefficients IfM,, V, are the molarity and volume of solution of A and M,, V; are the molarity and volume of solution’. -Then aM MM For example take an acid base reaction. Na,CO, + 2HCl —+ 2NaCl+.CO, + H,0 IEM,, Vj are the molarity and volume of Na,CO, solution and M,, V, are the molarity and volume of HCI solution then MM, _MiVp renin 2MV, = MV, For a redox reaction ‘2KMnO, + 5{COOH), + 3H,S0,—> K,S0, + 2MnSO, + 10CO, + 8H,0 ‘Redox reaction is in between KMnO, and oxalic acid. Their stoichiometric coefficients are 2 and 5 respectively tM, and M, are the molarity of KMnO, and Oxalc acid V, and Ve are the volume of KMnO, and Oxadie acid Then MY | In all experimental calculations molarity ofthe solution is used and not the normality Molar mass oftheacid ©) Equivalent mass of an acid = NESTS Oe Basiity of an acid is equal to the number of replaceable hydrogen atom in its molecule, (@) Equivalent mass of a base : Molar mass ofthebase Equivalent mass of a base = Mote mass oltistose + Acidity of a base is equal tothe number of hydroxy Ions given in solution by its one molecule. Equivalent of mass an oxidising agent : Molar mass of thecxiising agent No.of electrons accepted per molecde Equivalent mass of an exiising agent s calculated in the following way + Equivalent mass of KMnO, : Potassium permanganate acts as an strong oxidising agent in acide medium aecording tothe folowing equation | 2KMInO, + 3H,SO,—> K,SO, + 2MnSO, + 3H,0 + 5(0) ‘According to fonle equation | the solution is of known normality then the normality ofthe other soliton Eq, mass of an oxidising agent = MnO, + 8H’ + Se” —> Mn” + 4H,0 | al Le one molecule of KMnO, which contain one lon of MnO, accepts 5 electrons Thus equivalent mas of KO, = Moat mass ofKMEO, "158 93 5 n Inthe tration dite HS, wed HINO, i not used because it sa ato extant, Halo not wed because it react with KMnO, to give chlorine which is an oxidant in aqueous medium, | 2KMn0, + 16 HCI —> 2KCl + 2M, + 50 + BHO 1 ‘Apparatus : EN Burette, Burette Stand, Pipette, Conical Flask, Funnel, Wash Bottle, Reagent Bottle etc.try Chemistry : Physical Chemistry RS: A ton Prenedeal | ‘ACID BASE TITRATION AM Determination of the concentration (rent ofa given sod jon by trating aginst a Derminon of he conensaten eng of ghen dum hte ton by raat ps | THEORY ' Jn the tration of a suong ac with a strong base, the amount of acd and base becomes chemi q equivalent at the end point and the chemical reaction is called neutralization reaction, Near the end pein there is suden change inthe pH ofthe scuon If fer end point even a mall amount of tase/acd Is adéed the shtion woud become sight ane oracle respecte. nthe tration between ac acid ea ac) and sou hydrox rong tse fling elon aes lace Hel 00H COON MeOH), aye OE a0. COOH COONa 2 Oral acid ‘Sodium oxalate In this tration phenclphthalein (HPA is used as an indcatr, The concentration of unknown Sltin is oleate ng/L: Moly ofthe slain can be cleat by sng the formula 2M, Vy = aM, Vy ae where a, My, , are respectively basiy, molary and volume of ac used andy, M, and V are acy, Tmoany and volume especie of bse wed nthe tito, Molar mass of oxalic acid, (COOH),2H,O = 126 g mol" ‘Molar mass of sodium hydroxide (NaOH) = 40 g mol" Eun am Deterination of the rng ofa gen shton of ite iyckehlr cd by taint agua saad coluon of sodium carbonate, THEORY The srengh of hrchoric act is detrined ty ttreing Hagia snd sohtion of soi Carbonate The oloving reaction fakes lace: Ne,00, HCI > 2 NaCl + CO, + HO Tei sca rece ee ee ko Ut lee re ete bee Teas eopenttent alc, the tin felows the ual ou, Le, the gretonfurlhed ty te elon ofthe NTR cad cues ars cose agia When ta eas ig ese W aaed oo eta chic Soin Uae protons We cba ce) CREM GET otis Sd pont i Mar mass of Ne,CO, = 106 gel" - Nolo mast of Hel= 36.8910" am Determination of th drength of a ghen skin of de ychoelve sci by trating apa a servo sotaon of sob rae THeony hh soenth of teins acd 6 deterined by tatg tapaet 2 sini vk of sean bused hydroxide. The folowing reaction takes place: Nor rH nes Nacl HO INDICATOR Phere, END POINT — Colcuress soliton turns Into ight pink colour. Molar mass of NAOH = 40 g mol “Molar mass of HCI = 36.5 g mot" ieChemistry : Physical Chemistry REDOX TITRATION niin ‘A solution of ferrous ammonium sulphate (Moht’s salt) has been prepared by dissolving 17.0 gm in one litre solution. Determine the molarity and strength of the given solution of KMnOs with the help of Mohr’ salt solution. ‘THEORY : (Molecular equation 2KMnO, + 10FeSO,{NH),SO, 6H,0 + 8H,SO, ~> KSO, + 2MnSO, + 5Fe,(SO), + 10(NH),SO, + 68H,O (i) Tonte Equation MnO, + SFe* + 8H* > Mn? + Fe + 44,0 INDICATOR KMn0, END POINT : [At the end point almost coloures solution wl change into ght pink colour. ‘Molar mass of Mohr's salt FeSO, (NH,SO,.6H,0 = 392 g mol? ‘Molar mass of potassium permanganate (KMnO,) = 158 g mol AIM a self indicator. am mi Find out the concentration of potassium permanganate solution in gram per Iter. For this purpose you are provided with a standard solution of erytalline oxalic acid of molarity M/40. ‘THEORY : (Molecular equation : 2KMn0, + COOH) 24,0 + 3H,SO,—> K,$0, + 2MaS0,+ 10CO, +1840 (i) Tonic Equation: 2Mn0j +5C,0% +16H" -> 2Mn?* + 10CO, + 8H,0 INDICATOR : KMn0, is a self indicator END POINT: At the end point almost colourless solition wal change into light pink colour. Molar mass of Oxalic aid (COOH),2H,0 = 126 g mol1. ‘Ans, Determination of the strength of unknown solution with the help of a solution of known strength is called 2. ‘Ans. The solution whose strength is to be determined is called titrand, s: 4. Ans. Ans. 6. ‘Ans. The substance which indicate the completion of the reaction between titrand and titrant, Cy Ans. 8. Ans. Redox titration. 9. Ans. 10. Ans. 1. ‘Ans. Molar mass and equivalent mass both are 392g. 12. Why dilute H,SO, is added with preparing standard solution of ferrous ammonium sulphate ? ‘Ans. It is added to prevent the hydrolysis of ferrous sat. ‘Ans. The solution with the help of which the concentration of unknown solution is determined is called titrant. IMPORTANT QUESTIONS What is titration ? titration, What is titrand ? What is titrant ? ‘What is a standard solution ? ‘The solution whose strength is known, called standard solution. ‘What is the end point 2 The point in a titration at which the reaction just gets completed is called the end point. What is an indicator ? What is the indicator is KMnO, titrations? KMn0, in a self indicator. What is the type of titration between KMnO, and Oxalie acid ? What isthe minimum volume of solution which can be measured with the help of burette ? OL mL What are oxidising agent and reducing agent in the titration of Mohr’ salts and KMnO, ? KMnO, is an oxidising and FeSO,(NH),SO, 64,0 is the reducing agent. What are the Molar mass and Equivalent mass of ferrous ammonium sulphate ?ysical Chemistry Pre Medical (Enthalpy of solution of CuSO.) Tans Introduction ‘When a substance is dissolved in water or in some other solvent, heat is evolved or absorbed. This energy change depends upon the amount of substance and solvent taken. Therefore, it is necessary to mention the amount of solute and solvent. Generally, it has been observed that when the amount of solvent per molecule of solute is very high, no appreciable heat change occurs on dilution. Therefore, “The energy change taking place when one gram molecule of a substance is dissolved in excess of solvent such that on further dilution no change takes place is known as heat of solution.” Word ad is used when the Imit of dilution is crossed as it shows that water isin excess. Example- KCl (6) + aq —> KCI (aq) - 4,400 cal KOH (5) + aq —+ KOH (aq) +13,300 cal ‘Objective :To determine the enthalpy of dssohition of copper sulphate or potassum nitrte Requirements : Beaker, pipette, porcelain dish and thermometer. Theory :varit Hof reaction kochore i to be applied to determine the heat of solution. a aH 8 Re Where AH = increase in molar heat content (.e., negative value of heat of solution per mole) and S is solubility, Integrating equation (i) within the limit of temperature in which no appreciable change in heat of solution ‘occurs gives, 2. 2035( 3) - Where S, and S, are solubilities at temperature T, and T, respectively while Ris solution constant in calorie per degree per mole, Keeping R = 2 cal/mol K, heat of solution can be calculated. Procedure : (@ A saturated solution of copper sulphate is prepared at 55°C and is placed in a thermos flask with a ‘wide mouth. The temperature of the solution is allowed to fall slowly When the temperature falls to 50°C, a small amount of the saturated solution is pipetted (10 mi quickly in a previously weighed porcelain dish. “The dish is cooled at room temperature and weighed again, w wo) (iv) The dish is then kept on heated sand bath and the solution is heated to get dry residue. (The dish ts cooled in a desiccator and then weighed. Thus, from the weight of salt left in a known ‘amount of water in its saturated solution, the solubility of salt taken is calculated at 50°C a) Repeat the above steps at 45°C, 40°C, 35°C, 30°C and 25°C and find out the sokbilty Calculation : Now from equation (2) (refer theory) we get 08989 Ta 2 th Substituting S,, ST, T, value of AH can be calculated ituting S,, S,, Ty. Tp log, ~logs, =Chemistry : Physical Chemistry ALL ete PreWedeal Bales © Keep the temperature constant. If thermostats not avalable use thermo fas 2 clear supematant quid isto be taken inthe porcelain dish. Enthalpy of Neutralization : . Reaction between acid and base to produce salt and water is known as neutralization reaction. The energy Sosa ie hnoum as ently of anton, nother word eat changes tn oe when oe gram valent of an acid reacts with one gram equivalent of a base or vice versa is known as enthalpy of neutralization, can Example : HNO,aq) + NaOHlaq) —> NaNOJac) + H,0 +13690 cal When 63 gram HNO, (.¢. one gram equivalent is treated with 40 gm NaOH (Le. one gram equivalent, the solution becomes neutral and 13690 calorie of heat is produced. This is known as enthalpy of neutralization, Other examples : Hlaq)+NeOHag) —> NaCl) + H,0 + 13,680 cal Hefaq) + KOHlag) —> KCilag) + H,0 + 13,710 eal HClag) + LIOH(aq) —+ LiCheg) + H,0 + 13,710 cal ‘Acids and bases used in above reactions are strong and enthalpy of neutralization ts 13,700 cal Tn other words, the value of enthalpy of neutralization of strong acid and strong base is always 13,700 cal “This concept can be cleared by considering the theory of electrolytic dissociation. Suppose equivalent amount of strong acid HA and strong base BOH is dissolved in water, then HA + BOH—> BA + H,0 + 13,700cal 6 or H+ A’ +B'+ OH 9 B+ A" +H,0 + 13700cal Canceling common ions from both the sides 0 H’ + OH —+ H,0 +13700cal It means that enthalpy of neutralization of any strong acid and strong base is actually the enthalpy of formation of water and its value will remain constant for all strong acids and strong beses. Enthalpy of neutralization does not remain constant if either acid or base is weak. Its enthalpy of neutralization Is always less than 13,700 cal ne Example: Haq) + NH,OH(aq) —> NH,Clia) + H,O + 12800 cal (CH,COOH(eq) + NaOHlaq) —+ CH,COONalea) + H,O + 13,400cal, In these reactions formation of H,O by combination of H’ and OH! fons and dissociation of weak acid {or weak base) goes side by side. In this way, tonization enthalpy or heat of ionization is also involved in their ae tonizaion, If enthalpy of ionization of acd is Q calorie, then CH,COOH (eq) —+ CH,COO" + H + Q cal HY 40H —+H,0 + 13,7006a. nh [As shown above, enthalpy of ionization of acetic acid is 13,400 cal. Therefore, Q + 13700 = 13400 calorie Q = 13400 - 13,700 = -300 calorie “Thus, enthalpy of fonization of acetic acid fs -300 calorie. In other words, 300 calories of heat is absorbed forthe ionization of 1 gm molecule of acetic acd, Similarly, NH,OH(aq) —» NH,’ + OH" + eal. H+ OF —+H,0 + 13,700cal Q + 13700 = 12300 (= -1400 cal ‘Therefore, enthalpy of lonisaion of NH,OH is ~1400 cal pees AChemistry: Physical Chemistry (Enthalpy of neutralization of strong acid and strong base) neutralization of strong acid (HC!) and strong base (NaOH). Requirements : Calorimeter (or one thermos flask), thermometer calibrated to 0.1°C, two 250 mi volumetric flask, 250 ml of 1 N-HC1 and 250 ml of 1 N-NaOH solution. Objective : To determine the enthalpy of Theory : Equal volume of equinormal acid and bases are mixed in calorimeter and the temperature is recorded. By noting the maximum temperature attained during reaction, enthalpy of neutralization is calculated provided water-equivalent of calorimeter is known, Procedure : (Determine water equivalent of calorimeter as given below : Take 100 mi of water in a calorimeter and note down its temperature. Now take 100 ml water in a beaker and heat it. Note down its | | temperature of hot water and mix it to the cold water contained in the calorimeter. Note down the ‘maximum temperature of the mixture. (i) Now take 100 mi of N-NaOH solution in a thermos flask and note down its temperature. Add 100 ml of 1 N-HCI to it, stir it properly and note down temperature of the mixture. ] Observation : (1) Volume of cold water = 100 c.c. ‘Temperature of cold water t,°C Volume of hot water = 100 c.. ‘Temperature of hot water = °C ‘Temperature of mixture = (2) Volume of base = 100 c.c. Initial temperature of base = Volume of acid = 100 c.. Final temperature of mixture Increase in temperature = (t)~t,) °C Calculation : (1) Water equivalent (W) of calorimeter Increase in temperature of cold water = (ty ~ tC Decrease in temperature of hot water = (t, -t)°C Applying principle of calorimetry Heat gained = Heat lost Heat gained by the cold water + heat gained by calorimeter = Heat lost by hot water Now, heat gained or lost by a substance ‘= Mass x specific heat x rise or fall in temperature 100 x 4.2 x (t,~t,) + W x(t, -t) 100 x4.2 x(t, t,)Chemistry : Physical Chemistry Where Specific heat of water = 4.2 J/a/"C and W = Mass of calorimeter x Specific heat of ‘calorimeter and it is known or water equivalent of calorimeter. OF t,t) (100 4.2) + W] = 100 x4.2 x(t, -t) (100 x4.2) + w= 100%4.2x(t, —t) (4) 100x4.2x(t, ~t) eng) | 100 4.2) 170 w (2) Calculation of enthalpy of neutralization : Heat produced on mixing 100 c.c. each of acid and base Q. = Heat gained by acid and alkali + Heat gained by the beaker =200 x4.2 x(t, —t) + W x(t) = ty ‘Where total amount of acid + alkali = 100 + 100-200 ml or Q= (200 x4.2 + W) tt; ~t,) joules or — Q= xjoules say) ‘Since, x joules of heat is produced on mixing 100 ml of 1 N-HCl and 1 N-NaOH, therefore, the enthalpy of neutralization of HCl and NaOH is 10 x J/eq, Precautions : (0 Mixture should be shaken properly in themos flask. (i) Use a good quality thermometer for measuring terperature. (ii) The liquid should not spurt while mixing or stirring. (iv) ‘Temperature of acid and alkali should be same before mixing IMPORTANT QUESTIONS 1. What is heat of solution? ‘Ans. Heat liberated or absorbed when 1 gm mole of a substance is dissolved in excess of water is called heat of solution 2. What does ‘aq! mean? ‘Ans. When during the preparation of solution limit of dilution is crossed, word 'aq' is used. It means that water is In excess 3. What is enthalpy of neutralization? ‘Ans. Enthalpy change taking place when one gram equivalent of acid is completely neutralized by 1 gram ‘equivalent of base, 4. Which apparatus is used for determining enthalpy of neutralization? ‘Ans. Calorimeter. 5. What isthe value of enthalpy of neutralization of strong acid and strong base. Ans. 13,700 caloriesChemistry : Physical Chemistry (Preparation of lyophilic and lyophobic sols) eee SURFACE CHEMISTIO Colo S id's sat of substance which depends onthe particle sz, Cllotal sate an intermediate stat ween true solution and suspension. The radius of collokdal particle 10" to 10%em, Type of Solution | True sohation ] Colloid Suspension] | Radius of particles |< 107 am 10" to 10% em | Colloidal solution is heterogeneous and has two stales 7 1. Dispersed phase 2. Dispersion medium Both phases may have diferetdiferent solid, liquid and gaseous states. For example in sol, dspersed Phase is solid while dispersion medium is quid, Inthe same way i dispersed phase and dispersion median | ‘are liquid then the colloid is known as emulsion, | Sols are of two types : (9 Lyophilic sol. : In this type of sl particles of dispersed phase has afnity for dispersion medium. They are reversible and can be prepared easy. They are not coagulated easly, e.., colloid of starch, gum, | te } GLyephobic sol. : In this type of solution particles of dispersed phase has litle or no affinity for | dispersion medium. They can only be prepared by special method, They are easly precipitated, ¢g., sol of feric hydroxide, meta sl. ot: When dispersion medium is water, above sols are respectively called hydrophilic and hydro-phobic ‘| colloid. Methods of Preparation of Colloid } 1. Dispersion method : Particles of suspension are broken down Into coloidl sled particles wing | colloidal mil, electri are method or peptizaion, 2. Condensation method :Parices of rue sohtion are converted into collodl sized partes & ‘methods : By pasing vapours of substance through solvent, by excessive cooling or by changing the solvent ‘Chemical methods : Double dissociation, oxidation, reduction or by hydrolysis, Coagulation = Precipitation of colloidal sols known as coagulation. Coagulation of colloidal sol is done by following method (© By mutual precipitation : Coagulation takes place when two oppositely charged colloidal sohtions are mixed. (8) By mechanical agitation : Sol gets coagulated when it svigorously agitated mechanically (i) By heating : Sol gets coagulated when heated. (iv) By addition of electrolyte : Colloidal particles are charged. Hence, of electrolyte. Hardy-Schulze Law: For the congulation of a colloal particle, ion having charge opposite to that prosont con itis effective. Greater the charge more isthe effect. Therefore, they get coagulated on addition for the coagulation of negative colloid the decreasing order of elect of postive ion is | Al* > Ba” > Na* Jn the same way for coagulation of postive charged cold the efect of negatve ion decreases inthe onder PO," > 80," > Ct°o ng ent Chemistry: Physical Chemistry Object: Preparation of colloidal. sol. of starch (lyophilic sol). Requirements : Beakers (100 ml, 250 ml), testtubes, glass rod, wire gauge bumer, starch powder, distilled water, ete. Principle: Starch sol. isa lyophilc sol. Starch forms lyophilic sol with water at 100°C and it is stable at normal temperature. Procedure : Take about 1 gm starch powder and make paste with small quantity of water in a test-tube. Boil the water in a 250 mi beaker. Now add this paste or suspension of starch slowly ina thin current. Stir glass rod throughout the water. Boil whole solution about 5 minutes and keep it to cool. Cooling of the solution should be automatic and slowly dont use ice or shaking for cooling because it may cause precipitation Precautions: () Use distilled water as medium. Due to presence of ionic salts in ordinary water, coagulation may occur. (3) Paste of starch should be added slowiy. (ii) Stir the hot water continuously (iv) Be sure that there is no ionic compound which makes it unstable, Objective: Preparation of colli so of es burn, Requirements +2 beaters 250 m), ne mortar, asso, 2eage, dtd wate, Principle: Egy bum forms bophic sl wth unter trom temperature Procedure Bra the opps and coc he matali baker Now tner colors ogg abun in rather boner, hence separating it fom egg ya. Now aid dropwise 120m died ater neg albumin {and stir it continuously. Complete this process in 20 - 25 mins. Now fir the solution through fiter- paper. “This filtrate is colloidal solution of egg albumin. Precautions : Colloidal solution of egg albumin should be prepared in cold water because in hot water it cides Objective ; Preparation of ferric hydroxide sol, (lyophobic sol). —— barr, et 296 slain of ec clre nd data ster Peete Pec stone's bapa Hobe prope by byiconlsof fee clerde This method ie 8 conancaton scott sell pains f FeCl, + 3H,0—> Fe(OH), + 3HCL ee In this method, removal of HCI i eisntalubich be removed by day. Parcles of FeO, adsoro Fe" fon frm soon andl pores became pote charged Vessel which to be ‘cleaned by steamChemistry: Physical Chemistry Procedure : It invoves thre steps, 1. Cleaning of glasswares : All the glasswares are cleaned with steam process. Cleaning is done according to th following arrangement ~ Preparation of sol : Take about 150 mi dstiled water in conical flask and bolt In boing water add about 20 ml ferric chloride solution dropwise with the help of dropper. Heat the solution till it becomes red coloured. Now fer the solutions, 3. Removal of HCI : HCI formed in the process is removed by dialysis process with the help of parchment pape. Precautions : () All vessels or glasswares should be cleaned with steam (i) Always add FeCl, in boing ‘water. (ii) Ferric chloride should be added dropwise. (iv) Be sure that there is no ionic compound or ionic species present. HC’ should ako be removed Ea Objective : Preparation of colloidal sol of aluminium hydroxide, Principle : Aluminium hydroxide colloid is also lyophobic colloid. It prepared by adding aluminium chloride slowly in boling distilled water. AICI, +3H,O—> Al(OH), + 3HCI Remaining experiment is exaclly ike Experiment No. 3. Objective : Preparation of colloidal sol of arsenic sulphide (As,S)) Requirements : 2 beakers (400 mi, conical flask, Kipps apparatus, glass rod, rubber tube, cork, burner, etc. Arsenius oxide (As,O,), dsiled water, iron pyrite, di, H,SO,, CO, or H, gas. Principle : Arsenius sulphide colloid is hydrophobic colloid. It is prepared by condensation method i.e. double decomposition method by As,0, and H,S. As,0, +3H,S—> As,S, + 3H,0 Ie is yellow colour sol and particles possess negative charge. In colloid As,S, particles adsorb sulphide Jone (S*) which are obtained by ionisation of H,S, hence they possess negative charge. Procedure : Take 250 mi dstiled water in a beaker and add approximate 1gm of As,O,, Stir the solution while heating. When As,0, get dsohed in water then iter the solution. Cool the fiterate. Now pase H,$ as slowly through fterate. 5,0; solution IJ water ntl it help of boling chloride hide ions 2 solution pass H,S. Chemistry : Physical Chemistry Freeda) Solution tus yellow. After passing HS sulin, (oiton remains yellowish, no increase in colouration, ‘excess HS is removed by passing CO, or H, gas. Test it by lead acetate paper. It tums black in the Presence of H,S. If by passing CO, or H, gas in the solution, the paper remains asi s by expeled gos of Solution, it means solution is now free from excess H,S gas. Now solution is fered through fter-paper. This fterate is As,S, collod. Above coloid is purified by dais through perchment paper. Precautions: () H, gas should be firstly passed through water, then only it can be passed in the solution for preparing colloid At) "The solution should be cold while passing H,S gas otherwise precipitation of As,S, takes place. (Gi) Check removal of excess H,S gas from the colloid. Because presence of H,S makes colloid unstable and AAs,S, changes into precipitate. (iv) Purification of colloid must be one through dialysis for the removal of ionic substances, IMPORTANT QUESTIONS 1. What is colloidal solution? ‘Ans. Solution in which particle size of dispersed phase s 1 nm to 100 nm i called colloidal solution 2. What is lyophobie and lyophilic colloid? ‘Ans. Substances which do not form colloidal solution easily on mixing with aliquid is known as lyophobe colloid ‘while substances which easily attain colloidal state is called lyophilc colloid 3. What is coagulation ? ‘Ans. Precipitation of colloidal solution by loss of charge is known as coagulation. 4, How does charge on colloidal particle prevents coagulation? ‘Ans. Colloidal partices being like charge repels each other and thus prevents coagulation, 5. What is Hardy-Schulze rule? ‘Ans. Greater the charge on effective ion greater isis coagulation power or precipitation power. 6. How are colloids classified? ‘Ans. On the basis of physical state of dispersed phase and dispersion medium colloids are of following type Dispersion medium Dispersed phase Name of colloids Examples ro a tea on a jee Solid Solid Solid sol Alloy, gem | so Un a | aac Go Solid foam Pumice stone on sy aes Src Gas Liquid Liquid Aerosol Cloud, mist, fog 7. What i dialysis and what is its use ? ‘Ans. It is a method of purification of sol. Selective diffusion of particles of crystallold present in colloid through ‘animal membrane oF parchament membrane is known as dialysis 8. What is peptization? ‘Ans. The process of conversion of freshly prepared precipitate into colloid by shaking with an electrolyte is known as peptizationPre-Medical 0 w CHEMICAL KINETICS H,0, +21 +24" 2H,0+1, Procedure : Chemistry : Physical Chemisty Kinetic study of the reaction of iodide ions with hydrogen peroxide at room temperature) Object : To study the rate of reaction of iodide ions with hydrogen peroxide at room temperature using different concentration of iodide ions. Requirements : Four conical flask (500ml), measuring flask, burette, pipette (25m), etc. Chemicals required : 0.1M KI solution, 2M HCI solution, 4 volume of H,O, solution, 1M sodium thiosulphate solution (hypo), starch solution. ‘Theory : In acidic medium, hydrogen peroxide oxidises iodide ion Label four conical flask 1,2,3 and 4. With the help of measuring flask or pipette take 25ml, 50ml, ‘75ml and 100 ml of 0.1M KI solution in flask 1, 2, 3 and 4 respectively, ‘Add 50 mi of 2M HC? in al the flask. Make up the volume to 200ml by adding distilled water. (ii) Add Sml of starch solution and 2mi of 1M sodium thiosulphate solution in each flask. ‘Add 25 ml of '4 volume’ H,O, in flask-1 and stat the stop watch. Shake the flask and note down the time required for appearance of blue colour. (Repeat step (vl) With flask 2,3 and 4 also. Precautions : () Volume of the solution should be same in all the flask (i) Time should be noted as soon as blue colour appears, (ui) Other precautions are same as those of previous experiment Result : Rate of reaction increases with increase in concentration of iodide ions. Observation : Conical] or Mut| 2m [water | Stach | 1Msodium | 10,50 | Time ua = flask | sot. (my | HO | (my | sot. (mp | thiosulphate (4 vol. mp | *Bbssrance of blue (x) Sol tue (Sec.) 1 2 | 50 | 15] 5 2 25 1 | 2 so | 50 | 10] 5 2 25 ane] 3 | 2 |'5 | | 5 2 a 50 2 eee [4 [100 | 50 5 Zz = 1ty ) 1. | Chemistry : Physical Chemistry titration? (1) Ferrous ammonium sulphate (2) KMn0, (3) Both (4) None of these 2. In titration colourless solution will change into urn light pink colour that point is called - (1) Equivalent point (2) End point (3) Both (1) & (2) (4) None of these 3. Which is the minimum volume of solution which Om, wn the ccan be measured with the help of burette ? (1) 0.15 mi (2)1 mi 301m (4) 10 mi ‘Which meniscus in read in burette in case of KMn0, (1) Upper (2) Lower (2) Middle (4) None of these 5. What volume is taken by pipette? (1) 50 ml (2) 30 ml (3) 20 mi (@) Sm 6. Which of the following is used as an indicator in the titration of a strong acid and a weak base? (1) Methyl orange (2) Phenolphthalein (3) Thyrnal blue (4) Fluorescein 71. The ideal indicator for the titration of strong acid ‘and weak base should have a pH range between, 3-5 (24-6 @e-8 (7-9 8. Find the concentration of HCl, if 10 ml of 0.5 Ca(OH), is required to titrate 50 ml of HCL (10M Q1/5M 5M (10M 9. Which is the concentration of KI solution used in this experiment? 01M os @12 @10 10. What Is the concentration of Na,$,0, solution sed in this experiment? (10.02 04am (2)0.04M (4)4.0M 1 Used in this experiment? (1) 3% (2) 4% What Is the percentage of hydrogen peroxide | 12, 13, 14, 15. ALLEN’ Pre Medical Sena eek sens Which is the self indicator is used in redox | For a reaction of iodide ion with hydrogen peroxide at room temperature, what will be the order of reaction concerning iodide ion? (1) Second order reaction (2) Zero order reaction (8) Third order reaction (4) First order reaction ‘What is the colour of the starch iodine complex formed? (1) Yellow (2) Blue (3)Green (4) Red Assertion (A) : A lyophilic sol is more stable than Iyophobic sol Reason (R) : When compared to lyophobic sol, colloidal particles in Iyophilic sol are heavily hydrated (1) Both (A) and (R) are true and (R) isthe correct ‘explanation of (A) (2) Both (A) and (R) are true but (R) is not the correct explanation of (A) (@) (Alis true but (R) is false (4) Both (A) and (R) are false Assertion (A) : One part of micelles is Iyophilic fn nature Reason (R) : Micelles have a lyophilic group like COO (1) Both (A) and (R) are true and (R) is the correct explanation of (A) (2) Both (A) and (R) are true but (R) is not the correct explanation of (A) (3) (A)is true but (R) is false (4) Both (A) and (R) are false Lyophobic sols are easily coagulated as? (1) The particles present in them come closer and form aggregates, leading to precipitation (2) The particles present in them move farther ‘and form aggregates, which leads precipitation (3) The particles present in them come closer and do not form agaregates, leading to precipitation (4) The particles present in them move further and do not from aggregates, leading to precipitation to (3) 6% (4) 2%The reagent of known concentration which is taken in burette is fe () Tirana (2) Titration | eae (8) End point 45. The unknown solution whose concentration isto | bbe determined by titration is called | (1) Titan (2) Titration (9) Titrant (4) End point 4G. Process in which addition of titrant from burette into titration flask tl titrant react completely is 49. called 50. (1) Titrand (2) Turation (9) Tirant, (4) End point 47. Wf 20 ml of 0.25 N strong acid and 30 mi of 0.2 | NN of strong base are mixed, then the resulting | solution is, (1) 0.25 N basic (2) 0.2 N acidic (3) 0.25 N acidic (4) 0.02 N basic Chemistry: Physical Chemisty 10 ml of 10 M H.SO, is mixed to 100 ml 1M [NaOH solution. The resultant solution will be (1) Acidic (2) Neutral (3) Weakly alkaline (4) Strongly altaline ‘The equivalent weight of KMnO, in alkaline medium as an oxidant will be (1) 31.60 (2) 52.66 (@)79.00 (4) 158.00 Assertion 0 A a a 1 oft, | Ind is more suitable than first for ttation. Reason = Iti dificult to add titrant in ist. | (1) Both (A) and (R) are true and (isthe correct explanation of (A) | (2) Both (A) and (R) are true but (R) is not the correct explanation of A) (2) (A) is true but (Rs false (3) Both (A) and (R) are false | (Ensen p Ls ae ase as sfit3[ij2{2l;il2{ilta;2[ifi ie ag aOT aT | 2a | as | ea [as enemas | 27] 80 3T1{ij[i1[2}s[4al[3[2ra)s}2]4 aa [aaa a7 38] oa ae ras a as nessa aoa eiale2e| wie 2866s 36) tels ee ese er Tasy|ras | 50 I“ Chen tg Chena ALL Sa snes eon ro ———K“~ TRY QUALITATIVE ANALYSIS ; ® QUALITATIVE ANALYSIS (SALT ANALYSIS) |rwolves the identification of one’ aio (atide)and oie cation (basic Yadical inva Given salt: The anions and cations to be tested are as under: Anions. : CO%-, S*, NO3, CI”, Br, NO5, SO} Cations : NH, Pb, Cu, AI", Fe, Zn, Ni", Ca", Bat, Mg The detection of acidic and basic radicals can be carried out by the folowing methods: DRY TESTS : ‘These tests are done with dry salt: These tests are also called preliminaty tests: These tests though do Hot {ive conclusive confirmation yet provide valuable information about the radicals present in a salt Preliminary examination by dry reactions : Dry tests may be classified as follows: 1. Physical examination. Action of heat on substances. To observe: (i) Change in colour; Its testing. 3. Flame test. 4. Borax-bead test. 5. Charcoal-cavity test. Evolution of a gas and [Diy eis ave “ot always YOISbIS|SiRee”Ldenificalion “of Yadicals is not finally possible. But they give an {indication only about the presence ofa radical. WET TESTS : It involves ajstenatlc examination for acid and basic radicals’ These tests are perforimed In solution, They ‘epend upon the/eharacterisic (specific) reaction of anions and cations. PHYSICAL EXAMINATION : "Note the'éélour, smell, density and state ofthe salt.” Table : Colour of some salts [[SHING. | Expected Radical ==——SC*SY vi | Ble oF Bhish green E. 3, Note elf indeates the absence of Cu FE™) NF ete ‘Note the smel ofthe sl Ammonia! smell indieates the presence of ammonium fons NH + "Amorphous ea maybe a carbonate + Heavy salts contain lead or barium. Light or fluffy salt may contain carbonate: ‘+ Deliquesceitéotoured salt may have copper nitrate or ferric chloride. ~ ‘A daiquescet colorless salt may contain sin nitrate, caletum chloride or magnesium chloridechemistry : Inorganic Chemistry DRY eae the presence of some radical. So fe inch of salt in a dry test tube may give some cue regarding the ur and smell of the salt on heating it in a dry test tube, ae) ol a fe —— 1. Salt gives cralling sound | Borax bead | 3: Evolution of gas 1 (i) Colouriess and odourless gas, CO% (Carbonate) (i) Colours gas with smell like rotten eggs S* (Sulphide) Gi) Yellowish green ges with suffocating smell Ct (Chloride) (iv) Reddish brown gas with pungent smell | Nos or Br (Nitrate or bromide) () Violet vapour with pungent smell DETECTION OF ACIDIC RADICALS (ANIONS): | ‘The acid radicals are divided into the following three categories: © Acid radicals to be tested with dilute sulphuric acid (Weak group radical): | Coe, S*,NO; ] (8) Radicals tobe tested with cone. sulphuric aid on strong heating (Strong group radical) cr, Br, 1", NO; | | (i) Acid radicals to be tested by their individual tests (General group radical) : ‘soy FF lodide) J 1, WEAK GROUP _ 7 SN. | a Inference | Confirmatory Tests Iz = 2 A colourless gas with smell of rotten a Moisten a piece of filter paper with lead = cae tn) | pene sion and pace # ene | | | ee oa B. ‘A light brown gas aS, (a) Pass the evolved gas through ferrous | sulphate solution, it tums brown | (6) Mix the given salt or mixture with a | | lite of KI and add diute HS0, | Evolution of volt vapours } | | (6) “Place the piece of filter paper on the ‘mouth of test tube moistened with seluion of stare, potasium lode _ _and acetic acid it tums bie CalOH), +CO, —scaco, +4,0 (Cane wth ‘spe Re nsecChemistry : Inorganic Chemistry ALL Sonne However, ifthe CO, gas is passed in excess the milky solution becomes colourless due fo the formation of soluble caleium bicarbonate, CaCO, + H,0+CO, —+CalHC0,), ite pe sohibe (i) Test for Sulphide : Dilute H,SO, decomposes a sulphide sat to form HLS gas which smell ike rotten eggs. NaS + HS0,—+ NaSO, + HS ‘On exposure to this gas, the lead acetate paper turns black due to the formation of lead sulphide. PO(CH,COO), + HS —+PbS+2CH,COOH ck (i) Test for Nitrite - When a nite is treated with dilute H,SO,, i yields a colourless nitric oxide gas which in contac with oxygen ofthe air becomes brown die to the formation of trogen donde. ‘2NaNO, + H.SO,—» NaSO, + 2HNO, Niro SHINO, —+ H,0 + 2NO + HNO, 2NO + 0,—» 2NO, Bron urd os (2) Onppassing the gs in dite FeSO, solution brown coloured comple sl formed FeSO, 7H,0 + NO —>IFe(H,0),NOISO, + 2H,0 Brod (©) When @ mixture of iodide and nitite is acted upon by due H,S0,, the fd ts docomposed ging violet vapours of dine 2NaNO, + H.S0,—» NaSO, + 2HNO, i 2KI + H,S0, —» KSO, + 2HI : 2HNO,+2HI—> 24,01, +2NO ins | Mkt tare "| 2. STRONG GROUP ead the | ‘SN. | Observation Inference | Confirmatory Tests 1. | Rcaloress or yeowsh geen gs wth | Cr, | Pa a gls rod dipped in NEH,OH atthe =| pungent and suffocating smell. ‘ ‘mouth of test tube. White dense fumes. ial Z [A bow go wih pungent and] Bc, [Sak » MnO, + Cone HO, and Fest | suffocating smell. - strongly. Reddish brown vapours with | pungent and sffcating sme | [S| iekt venous wih pungent on] gf, | Apichof ato, + suffocating sel Conc. H,S0, and Heat strongly. Violet | vapours which turn starch paper blue. a Ta. boon was wih pnsen we] NO |S + Cone SO, + Co cine r ieotia Gna (vtsis) | pallet. Heat strongly. A reddish brown tums L tas withpangent od sifeating sme | (Test for Chloride + Colouess pungent fures of hydrogen chloride ere ered on heating the sodium chloride wth cone, H.SO, NaCl + HSO,—+ NeHSO, + HC! sc 5chemistry: Inorganic Chemisty ‘Yellowish - green gas of chlorine with sulfecting odour is evolved when the solid chloride mixed with ‘Manganese dioxide is heated with conc. H,SO,. NaCl + H,S0,—> NaHSO, + HOL MnO, + 4HC|—+ MnCl, + 2H,0 + Cl, ‘The gas evolved by heating chloride with sulphuric acld forms white fumes of ammonium chloride with NHOH ) NHOH + HCl—> NH,Cl+H,0 ‘hie fames ‘The gas evolved by heating chloride with H,SO, forms a curdy precipitate of sliver chloride with ster ane dca | AgNO, + HC1—> AgCl+HNO, | Pot © (@) Chromyl chloride test: When solid chloride is heated with conc. H,SO, in presence of K,Cr,0,, deep red vepours of chromyl chloride are evolved, NaCl + H,S0,—» NaHSO, + HCL K,Cr,0, + 2H,S0, —+ 2KHSO, + 2Cr0, + H,O | C10, + 2HCI—> C10, Cl, + H,0 (Cvor horde When these vapours are passed through NaOH solution, the solution becomes yellow due to the formation of sodium chromate. | Cr0,C1, + 4NSOH—+ Na,CrO, +2NaCl+2H,0 ‘Yelow colour ‘The yellow solution is neutralised with acetic acld and on addition of lead acetate gives a yellow ‘precipitate of lead chromate. Na,CxO, + PHICH,COO), —> PbCrO, +2CH,COONa Yalow pb (1) Test for Bromide : Reddlsh-brown fumes of bromine are formed when the sodium bromide is heated with cone. H,SO, NaBr + H,SO,—> 2NaHSO, + HBr 2HBr + H,S0,—> Br, + 2H,0 + SO, (@) The aqueous soltion of bromide gives pale yellow precipitate of siver bromide which dissolves in excess of NH,OH forming a soluble complex. [AGB is sparingly soluble in NHOH solution) NaBr+ AgNO, —-+ AgBir+ NaNO, Pak yelow pt ‘AgBr + 2NH.OH —> Ag(NH),Br+2H,0 ; (©) When the fresh salt or mixture i treated with dilute H,S0, CHCl, or CCl, and chlorine water, chlorine ‘replaces bromine and the liberated bromine dissolves in CHC, or CC\, layer giving It brown coloun 2KBr + Cl, —> 2KCI + Br, Br, + chloroform —> Brown layer (i) Test for Iodide ; Violet vapours of foie are evolved on heating iodide with concentrated H,SO, 2K1 + 24,50, —+ 2KHSO, + 2H 2H + H,S0,—+ 1, + $0, + 2H,0 (@) Violet vapours with starch produce bue colour, 1,4 Starch —> Blue colourle er ep he Ee Chemistry : Inorgar Chemistry (©) Aqueous solution of the iod not dissolve in NH,OH, Pre Medical ‘ives yellow precipitate of Agi with silver nitrate solution which does Nal +AgNO,—> Agi + NaNO, ‘Yelow pot ‘When the glven substance is treated with dite H,S0,, CHC, or CCl, and chlorine water, chlorine replaces iodine which dssolves in CHCl, of CCl, layer giving it violet colour. 2KI + Cl —> 2KC1+ |, 1, + CHC, —+ Violet layer (IV) Test for Nitrate : Light brown fumes of nitrogen dioxide gas are evolved on heating the nitrate with concentrated H.SO,, @ NaNO, + H,S0,—> NaHiSO, + HINO, 4HNO, — 24,0 + 4NO, +0, These fumes intensfy when copper turings are added Cu + 4HNO, —> CuINO), + 2NO, + 24,0 Ring Test : When the aqueous solution ofthe substance is treated with freshly prepared solution of ferrous sulphate and cone. H,SO, a broum ring is formed on account ofthe formation of a complex at the junetion of tw liquids NaNO, + H.SO,—+ NaliSO, + HNO, 6FeSO, + 2HNO, + 3H,SO,—+ 3FeS0), + 4H,0 + 2NO [FelH,0) 180, H,0 +NO—>[FelH,0),NO}SO, + 24,0 fete aie ‘ot fea (9) GENERAL GROUP Some anions ae dented by their characteristic chemical reactions (© Test for Sulphate : Dissolve litle amount ofthe substance (salt or mixture) ind, HCl and add bratium chloride sltion and formed white precipitate of BaSO,. A white precipitate insoluble in cone HINO, is formed. Reactions with explanation : White precipitate of barlum sulphate is obtained when solble sulphate i tested with barum chloride solution Na,SO, + BaC, —> 2NaCl + BaSO, ‘The white precipitate is insoluble in cone. HNO,, Certain chlorides e.g., NaCl and BaCl, when present in large quantities, may form @ white precipitate which dissohes on dilution with water. Silver and lead, if present, may be precipitated as silver chlorides and lead chloride by the addition of barium chloride, To avoid it, barium nitrate may be used in place of barium chloride Wdentification of basic radicals = For systematic analysis, the basle radicals have been clasiied into groups. Eaci group has a reagent which shows the presence of the basic radical belonging to that particular group. Its necessary that the radical Is. completely removed inthe respective group by using excess of group reagent, otherwise its presence creates dificuity in higher group. ——— ee‘chemistry : Inorganic Chemistry DETECTION OF BASIC RADICALS (CATIONS) Group | Cations | Group Reagent | precipitate formed with colour ] Ze | NH; | NaH on botng [No ppt. but ammonia gas is formed 1 | 7 | Pe OS + dilute HCI OCI, - White | c Cv | H,S gas in presence of di. HCI CuS - Black | | : | m | Fe Fe(OH), ~ Reddish brown | jy | NH,OH in presence of NH,Cls) | | \ a AVOH), - White gelatinous | | wv | one IS - Black H,S in presence of HOH | 2a" ZnS ~ Dirty white or slate ike | vo] pe 7 Ba00,-White | : | (04,60, pres NHLOH Catt CaCO, - White | | - oe | Mg | NeJHPO, solution + NH.OH + NH.CI_ | Mg(NHJPO, — White anes | [PREPARATION OF ORIGINAL SOLUTION (0.5) —] | For performing wet tests of basic radical, the original solution ofthe salts prepared in the following order: (Sallis shaken with distilled water in cold or on bolin. (i) Salt is treated with dil, HCl in cold and then on heating, (i) Salt is treated with cone. HCl in cold and then on heating "Note: Test the ammonium (NH, radial in zero group immediately after detection of acidic radials and before doing wet tests of basic radicals in verlous groups. 11. Why HCl is added before pass H,S gas to precipitate Il group ? | ‘Ans. Sulphdes ofl group have low subi product. To preipltate them lesser concentration of sulphide ions s needed. To rece the foisation of HS gas HCl sada Deca it has a common ton ae (' hychoge ton, 2. Why the ftrate of group is boiled with HNO, beore the pretation of Il group? | ‘Ans, To oxidise ferrous in to fee ions tao help in the removal of H,S ges from the firae, 3. Why NH{Cl\s added before adding NH,OH in Il group ? Ans. To redice the concentration of OM'by common ton (NH;) effect so that the hyhoxiles of 2n, Mn, Ca, Ba, Mg ete. may not be precipitatedzens Pate ofa wie a > ain [ Colour offlame observed | Colour of flame observed | Inference ] — through cobalt glass ___| Blush green [ Berium salts [Brick red Light green (Calcium sats 7 (i) [Intense blue surounded by green flame | Same colourvsble | Copper ats 2. BORAX BEAD TES! ‘This testi caried out only coloured salts, For this, make loop at the end of platinum wire. Hat the loop in the Bunsen flame tilts red hot. Dip it in the sat and heat again. Note the colour of the bead. onder Fe, Bora Bend test Gola ofthe ed in Ons | Colour fh bad in cing Bae ] fame errkmina) | | Is and ‘When hot ‘When cold Wher ‘When cold Green [Blue Red es a Se ons 3. CHARCOAL caviry TEST ingen Toke pinch ofthe st Mic wall wth an equal amount of fson mixture (e,CO, + K,CO). Mosten wth drop of wte and fin cavity of charcoal Hock Heat tin reducing now) fame withthe ip of bow pipe Observe the fomaton of bead { Colour of the residue ~_| Inference Blue AP - oa xides of ‘Green m Zn a — Mechemistry: Inorganic Chemistry Flow Chart (Original Solution au Hct Precipitate, Group | no precipitate is formed Pb") as chloride Pere ee Preciptate, Group 1 1 no precipitate, take original solution (cry as sulphides thoy ced sited NAS Nilo i xa Preciptate, Group I In precipitate Fe*, AD as hones Pass | fore oot woke | nar al | Preciptate, Group 1V Iino precipltate, take orignal solution NF, 20") ‘ASE NH,OH wr as sulphides Sta NEC, Precipitate, Group V lf no precinitat, take orginal Ba", Ca") solution to tes Group VI, {a5 carbonates Mg" ZERO GROUP ‘Ammonium (Test for NH,) : Take the salina tes tube and add 2:3 mL. NaOH solution and heat. I the smell of NH, i observed, it confims the presence of NH; radical. The confirmation can futher be done by the following test. “The substance (sat) when heated with NaOH solution evolves ammonia, NH{Cl + NoOH—> NaCl + NH,+ HO ‘When a rod dipped in HCLis brought on the mouth ofthe test tube, white fumes of ammonium chlorde are formed NH, +HO—> Na | To the aqueous soliton of ammonium sl when Nene’ reagents adde, brown coloured preciptate «| i formed. A Ha 2K Hal, + NH,CL+ 4KOH—> "So + 7H1+ Ke1~ 34,0 co ; it ir | crouP Radical : Po Group reagent : Di. HO. Procedure: Tae cold dite orginal sohiton and add fw drop of dite HCL. white preciptate appears, add more of dite HCL If wht precipitate appears, add more of dle HC as to complete mers basic radeals of frst group, Fier, keep the filrate fr sibsequent groupe,ty Chemist organic Chemisty ALI Se, EE Po, + 2KCL Get scion) Yelow precipitate This yelow precipitate (Pb sslube in boing water and reappears on cooling as shining crystals 2. On atktion of potassium chromate (K,CrO) solution a yellow preciptate of lead chromate biained. This confims the presence of Pb ions + KC, —+ — PeCI0, + 2Kel ‘ead eromate (Welow prectate ‘The yellow precipitate (PECIO) is soluble in hot NaOH solution PeCrO, + 4NaOH—> Na[PO(OH),) + Na,CrO, Solum ti Tyconophante 3. A.white precptate of lead supate (PESO, is formed on aditon of akohol followed by dl. H.SO, POC, +HSO, —> PASO, + 2HCI Lead pate (Write preciptate) Lead sulphate is soluble in ammonium acetate sohitton due to the formation of tetvaacetatophumbatel ons ‘This reaction may be promoted by adion of few drops of acetic ac PbSO, + 4CH,COONH, —+ _(NH,,{PbICH,COO), + (NH),SO, Pec, (Hot sation) tthe ‘Anonin ts tence) cRour Radical : Cu" cee Group reagent: HS gain presence of i. HCI Procedure : Warm prt ofthe fae of ist group oF orginal slton containing dt HCl st group is absent and pss H.S gus. aback prepa spears 1. Test for Copper ion (Cu) ae (a) Copper sulphide dissolves in nitric acid due to the formation of copper nitrate. CAS + BHINO,—> 3CuNO}, + 2NO + 35 + 440 (On heating the reaction mixture for long ine, sulphur i xed oaulphate and copper phate formed and the soliton tums hue. A small amount of NH,OH precpates base conver sate which sohble in exces of ammonium hydroxide due tothe formation ef tevearminecopper complex S++ ZHNO,—+ 1150, +2NO 20." + $0," + 2NH, + 21,0 —+ CuO, CSO, + 20g Tease A aan (CuOH,ca80, + BNF, —+ 210UNHJS0, « 2087 50, ation of Tessrmincoper sulphate Deep blu) aeLEM Chemistry : Inorganic Chemistry = |)/ Pre-Medical ) Te, sliton on acetone a an then ar pts ees RIFE) 'on gives a chocolate colouration due to the formation of copper ferrocyanide le. CaPeICN tion due to the formation of copper ferrocyani peas ON + 4CH,COOH —+ CuSO, + 4CH,COONH, uSO, + _ KJFe(CN) —>CulFe(CN\] + 2K,SO, Potts Copper) hevacyenofenate 09) heracysnoferate (Chocolat brow preiiate) nour mi Radicals : Fe” and Al* Group reagent : NH,OH + NH,CI Procedure : Boil off HS from the ftrate of II group or take orginal solution, if first and second group N radials are absent, Add few drops of conceniated HNO, and boll the sliion. Add sold ammonism chloride and ammonium hydroxide slowly till the solution smells of ammonia. f the precipitate appears, fier. ‘Test for ferric ions (Fe™) Reddish brown precipitate of feric hydroxide dissolves in hydrochloric acid and ferric chloride is formed. Fe(OH), + 3HCI—> FeCl, + 3H, (@) When the solution containing ferrte chloride is treated with potassium ferrocyanide solution a blue pprecipitate/colouration is obtained. The colour of the precipitate is Prussian blue. It is fer ferro-cyanide. The reaction takes place as follows: 4FeCl, + 3KJFe(CN]—> FeFe(CN), + 12KCL Potassium Prussian blue ferecyanide precipitate If potassium hexacyanoferrate (I) (2. potassium ferrocyanide) is added in excess then a product of composition KFelFe(CN)] is formed. This tends to form a colloidal solution (soluble Prussian blue’) and cannot be filtered. FeCl +KjFe(CN] —> _KFelFe(CNiJ + 3KCI (Sokible prin ue) (0) To the second port ofthe solution, ad potassium thoevante(potasum suiphocjanie)soltion. The appearance ofa blood red colouration confirms the presence of Fe” fons. Fe" + SCN'—> [Fe(SCNI Blood rd colour “Test for Aluminium tons (AP) a mks crit Win MB ADs cess awit etre ncn hero formed whch soe nce f som hone sean | ar te formation of sadam meta suite ING, # SNGOH —» AIOH}, + SNC! AIO}, + NaOH —» NaAlO, + 24,0 pores ‘White gelatinous ‘precinlate ‘peta kumi ne soon test when bse mus i aed 0 the ston, 2 re colouration obained duet the ao ere ofthe soliton, On addon of NH,OH soliton drop by drop, the scion becomes a wand aluminum hydroxide Is preiated, Aluminium hydroxide adsorbs bu colour para oer vd forms inslible esorpion complet ramed ‘ake’. Thus a be mass floating in the shuton is obtained. The ts therefore called lake tes @ colourless 5