DALTON’S ATOMIC THEORY An atom is the smallest particle of an element which is neutral in nature, retains all the proper- ties of the element and takes part in a chemical reaction. The word atom was introduced by Dalton (alamos means undivided). ‘The Dalton’s atomic theory was proposed by Dalton on the basis of laws of chemical combi- ‘nation, Main Assumptions = Matter (of any type) is composed of atoms. = An atom is the smallest, fundamental, undivided Particle. = An atom can neither be created nor destroyed. = Atoms of an clement have similar size, energy and properties while atoms of different element differ in these aspects = Atoms combine in whole number ratios to form a molecule, therefore, a molecule is the smallest identity that exists individually. Modern view about the atom According to the modem view: = An atom is divisible into other smaller par- ticles which are known as subatomic particles It can also combine in non-whole number ratio as in the case of non-stoichiometric compounds (Berthollide compounds) like Fe, ,,O. = Atoms of same element also differ in mass and mass related properties as in the ease of isotopes1.2 _™ Mole Concept and Stoichiometry Molecule ‘he term molecule was introduced by Avogadro, It is the smallest particle (identity) of mat- ter that can exist independently and retains all the properties of the substance. Normally, the diameter of the molecules is in the range of 4~20 A and the molecular mass is between 2-100. In case of macro- molecules, the diameter is in the range of 50-250 A and the molecular weight may be in lakhs Berzelius Hypothesis According to the Berze- lius hypothesis, “Equal volumes of all the gases contain same number of atoms under the similar conditions of temperature and pressure.” This hypothesis on applica tion to law of combining volume confirms that atoms are divisible which is in contrary to Dalton’s theory. AVOGADRO’S LAW = Avogadro's law explains law of combining volumes, = According to this law, “Under similar conditions of temperature and pressure, equal volume of gases contain equal number of molecules.” It means 10 ml of H,, ©,, Nor a mixture of gases have same number of molecules It is used in () Deriving molecular formula of a gas (i) (ii) Determining atomicity of a gas Deriving a relation molecular mass = 2 vapour density M=2% VD. Deriving the gram molecular volume dv) = Avogadro number (N° or NA) = 6.023 10®. = Avogadro number of gas molecules occupy 22.4 litre or 22400 ml or em’ volume at STP. = The number of molecules in | em’ of a gas at STP is equal to Loschmidt number, that is, 2.68 = 10 = Reciprocal of Avogadro number is known as Avogram, MOLE = Mole is a unit which represents 6.023 x 1023 par- ticles, atoms, molecules or ions ete., irrespective of their nature. = Mole isrelated to the mass of substance, the volume of gaseous substance and the number of particles Ww Mole = 47 Wt. of substance in gm. Molar mass of substance ([Link]) Here G.m.m. = Gram molecular mass _ Volume of substance in litre ai 4 litre Volume of one mole of any gas is equal to 22.4 litres of dm’ at STP. It is known as molar volume Number of identities Mole = ‘Avogadro's number Mole= fy Here P= Pressure in atmosphere V= Volume in litre ‘T= Temperature in Kelvin R= Universal gas constant Relationship of Mole: Amole of any substance (like N,) stands for: = 6.023 = 10® molecules of N, m 2 6.023 = 10” atoms of nitrogen = 28 gm of nitrogen m= 22.4 litre of N, at STP. To Find Total Number of Identities = Total number of Molecule = mole(n) x N, @ Total number of Atoms = mole (n) = N, = No. of atoms present in one molecule = Total number of Electrons = mole (n) x N, « No, of electron present in one electron = Total charge on any ion = mole (n) « N, x charge on one ion * 1.6 x 10°C Illustrations 1. Ifa piece of copper weights 0.635 g, how many atoms does it contain?Mole Concept and Stoichiometry ™ 1.3 Solution Number of moles of Cu in 0.635 g 107 mol As | mole Cu contains 6.023 = 10* atoms of Cu So 10 mole Cu contains 6.023 10" 10° = 6.023 = 10" atoms of Cu 2. Oxygen is present in a one litre flask at a pres- sure of 7.610" mm of Hg. Calculate the number oxygen molecules in the flask at 0°C Solution PV =nkRT 76 « 10" 760 =n x 0.0821 L atm K* mol" x 273 K atm «11 x 7.6 « 10" L atm 760 * 0.0821 L atm K' mol x 273 K Number of molecules = (6.02 « 108 mol) (10"/22.41 mol) = 2.68 x 10 3. Calculate the total number of electrons present in 1.6 gram of methane. Solution Molecular mass of methane = 16 g mol" As 16g CH, contains 6 02 * 10® molecules of CH, So 1.6 g CH, contains 6.02 * 10® molecules of CH, As one molecule of CH, contains (6 + 4) = 10 electrons, so 6,02 » 10 molecules of CH, contain 10 x 6.02 = 10" = 6.02 « 10% electrons. 4. How many years would it take to spend Avo- gadro number of rupees at the rate of 10 lac rupees per second? Solution As Avogadro number = 6,023 « 10” So total rupees = 6.023 = 10 Rs Rate of spending = 10 lac rupees/s = 10° Res Number of years to spend all the rupees 7 6.023 = 10" Rs TO = 60 = 60 « 24 = 365 Rsiyear = 1.90988 * 10" years 5. Calculate the number of atoms of oxygen pres- ent in 88 g of CO, What would be the mass of CO having the same number of oxygen atoms? 88 Solution Number of moles of CO, = Bamr =2 moles As one mole of CO, contains two moles of oxy- gen atoms, so two moles of CO, contain 4 moles of oxygen atoms * 6.023 = 10% = 2.5092 « 10" Number of oxygen atom: As | mole oxygen atom is present in 1 mole of CO so 4 moles oxygen atoms are present in 4 moles of CO, Its mass is 4 (12 + 16) = 112 g 6. How many atoms of carbon has a young man given to his bride-to-be if the engagement ring contains 0.5 carat diamond? (1 carat = 200 mg) Solution Mass of diamond (C) = 0.5 * 200 mg = 100 mg = 100 x 107 g=0.1 g ra Ole Number of mole of © = 77 apo? = 1/120 mole mabe «108 Number of C atoms = 73 * 6.023 « 108 = 5.02 « 10" 7. If the Faraday were to be 60230 coulombs inste of 96500 coulombs, what will be the charge on an electron? Solution One mole clectron carries | Faraday charge As 6.023 = 10” electrons carry = 60230 C = 60230 So | electron carries = 7593~ 195 =1e10-"C1.4 @ Mole Concept and Stoichiometry MASS Mass can be expressed in terms of atoms or mol- ecules as follows: Atomic Mass isthe relative mass of an atom which shows how many times an atom is heavier than 1/12 mass of C-12. = The atomic mass of any element expressed in grams is called GAM. (gram atomic mass) Atomic mass = E * V ne @ Atomic mass ~ Specific Heat in cal, Itis known as Dulong Petit’s law Molecular Mass Molecular mass represents the total mass of a mol- cule, that is, number of times a molecule is heavier than that of 1/12 weight of C-12. @ It is non-variable. @ It is now called relative molecular mass. Determination of Molar Mass Its possible by these methods Vapour Density Method Vapour density of a gas is defined as the ratio of the weight of a certain volume of the gas to the weight of the same volume of hydrogen at the same temperature and pressure. Vapour density of a gas ___ Weight of “V’ litres of the gas ~ Weight of V" Titres of H, at the same temperature and pressure Suppose ‘V" litres of the gas contains ‘n* molecules Vapour density of gas _ Weight of ‘n’ molecules of the gas ~~" Weight of 'n’ molecules of H, _ Weight of 1 molecule of the gas ‘Weight of | molecule of H, 1, Weight of 1 molecule of the gas “2* Weight of | atom of H, W = 22400 VD. = Tohume at STP (in ml)” Here W = Weight of substance in gm. Molecular mass = 2 * Vapour density Graham Diffusion Method rir, = V(MJM,) Here r,, r, are rates of diffusion for two species while M,, M, are their molecular masses respec- tively. ii) By Colligative Properties Methods: xv=- Wer Here x= Osmotic pressure in atm V = Volume in litre W = Weight in grams R= Universal gas constant T = Given temperature m= Molar mass Illustrations 8 The weight of one litre sample of ozonized oxy- gen at NTP was found to be 1.5 g. When 100 ml of this mixture at NTP were treated with terpen- tine oil, the volume was reduced to 90 ml. Hence calculate the molecular weight of ozone. Solution Volume absorbed by terpentine oil = 10 ml As volume of ozone = 10 ml (as terpentine oil absorbed O,)Mole Conce pt and Stoichiometry = 1.5 So Volume of O, = 100-10 = 90 Mol. wt. of ozonized oxygen = WRT _ LS « 0.0821 «273 PV T xT =33.62 As volume or mole ratio of O, and O, is 900 : 100 So mol. wt. of ozoniz ed oxygen = 900 x 32+ 100 x X 1000 — 900 * 32+ 100 xX 33.62 1000 X= 482 Hence mol. wt. of ozone = 48.2 Equivalent Weight = Equivalent weight is the weight of an element or a compound which combines with or displaces 1,008 part by weight of H, or 8 part by weight of 0, or 35.5 part by weight of Cl, = Equivalent weight is a number and when it is denoted in grams, it is called gram equivalent. = It depends upon the nature of chemical reaction in which substance takes part. Methods to Find Equivalent Weight () For Acids é Molecular weight Protoeity or Basicity of Acid For example, for H,PO,, E = M/3 For H,SO,,E=M/2 (i) For Bases " Molecular weight Keidity or number of OF ions For example, for Ca(OH),, E=M/2 For AKOH),, E = M/3 (iii) Forlons Molecular weight Charge on ion For example, for SO, E = M/2 For PO,-,.E=M/3 (iv) For Compounds Molecular weight E = Valency of cation or anion For example, for CaCO,, E = M/2 AICI, E=M3 (v) For Redox Reactions Molecular weight Change in oxidation number For example, for KMn0, (a) In acidic medium: E = M/S KMn0, +3H,S0, > K,SO, + 2MnSO, +3H,0+5 [0] 5 unit change in oxidation number. (b) In basic medium: E = M/1 2kMn0, +2KOH > 2K MnO, + H,0 + [0] cone unit change in oxidation number (6) In neutral medium: E = M/3 2KMnO, + H,0 + 2KOH + 3Mn0, + 3{0] 3 unit change in oxidation number (vi) For Acidic Salt m Molecular weight Number of replaceable H-atoms For example, for H,PO, Ca(OH), + H,PO, — CaHPO, +2H,0 E=M21.6 ™ Mole Concept and Stoichiometry (vii) Some other methods (a) Hydrogen displacement method p= 211200 Volume of H, at NIP (b) Oxide formation method z= Wt of metal, Wi of oxygen Weight of oxygen = weight of metal oxide ~ weight of metal (©) Chloride formation method: = Wofmetal_, E="We of chloride * 355 Weight of chloride = weight of metal chloride — weight of metal (@) Double decomposition methods Eq. wt of salt taken _ Wt of salt taken Eq, wi of salt ppt WE of salt ppt (e) Metal displacement methods Illustrations 9, Find the equivalent mass of H,PO, in the reaction: Ca(OH), + H,PO, — CaliPO, + 2H,0 Solution As in this reaction only two hydrogen atoms are replaced so its equivalent mass will be given by the following expression Equivalent mass of H,PO, _ Molecular mass of ~ 2 = BL = Fea 10, On heating 0.199 g of a metallic oxide in a current of hydrogen 0.045 g of water is formed, Find the equivalent weight of the metal Solution Weight of Metallic oxide = 0.199 g As 16 g oxygen is present in = 18 g H,O So O, present in 0.045g H,0 = 180.045 0.042 ‘Weight of metal = 0.199 - 0.04 =0.159 Equivalent weight of metal = 2.459% 8 =318 11. 4.215 g of a metallic carbonate was heated in a hard glass tube and the CO, evolved was found to measure 1336 ml at 27°C and 700 mm pressure. Whaat is the equivalent weight of the metal? Solution Metallic carbonate — metalllic oxide + CO, 44 1120 wi. of Co, = a0 =228 Wt. of metallic oxide = 4.125 -2.2 = 2.015 g By law of equivalent Hence, E (eq. wt. of metal) = 12.58 Chemical Formula ‘A chemical formula represents the combination of atoms of all the elements which makes up a compound It represents the relative ratio of atoms of its constitu- ent elements, In case of a compound, it represents one molecule, one mole, one gram molecular weight of the compound Example, S, represents one molecule of phosphorous and one mole of phosphorous. Example, CuSO, 5H,O represents one molecule, one mole and one gram molecular weight of hydrated copper sulphate. Empirical and Molecular Formulas Empirical Formula It gives the simplest ratio of the number of atoms of different elements present in one molecule of a com- pound. It does not represent the actual number of atoms of different elements present in one molecule of the compound. Calculation of the Empirical Formula: i involves the following steps, one by one:(i) First determine the percentage composition by weight of each element present in the compound, 2 wt. of CO, 4 * wi of organic comp. * !0 wt of HO TS wt. of org. comp. * aly loo Duma's method __og_, Volume of N, at [Link] N%=73400 * wt of Org. comp” oR Vol of N, at STP. ¥* Wiof Org comp Kjeldahl’s Method 14xNxV N%= Wiof org. compound Here N = nonmality of acid the used to neutralize ammonia V = volume of acid the used to neutralize ammonia (ii) Now the percentage of each element is divided by its atomic weight to get the relative number of atoms of each element ‘These relative numbers obtained are divided by smallest number to get the simplest ratio numbers. (iii) iv) If the simplest ratio number is not « whole number it should be multiplied by a suitable integer to get a whole number. The ratio of these simple whole numbers gives the empirical formula of the compound. wv Molecular Formula It shows the actual number of atoms of different ele- ments present in one molecule of the compound. Molecular weight = 1 Empirical formula weight = Molecular formula = empirical formula * n. Mole Concept and Stoichiometry = 1.7 = Molecular weight of a substance can be deter- mined by methods like Vapour density method, Elevation in boiling point method, Depression in freezing point methods ete = The molecular weight of volatile compounds is determined by Vietor Mayer's method @ Molecular Weight = 2 « Vapour density = Molecular weight = empirical formula wt. « ‘n’ = For some compounds the molecular formula and ‘empirical formula may be same also, Illustrations 12. Acertain organic compound was found to contain 33.6% C, 5.6% H and 496 % chlorine. Find the empirical formula of the orgenic compound Solution Element % Atomic ratio Simplest Ratio c 338 33.8/12=28 2807=4 56 S6=56 56/0.7=8 cl 49.6 49.6/35.5=1.4 1.4/0.7 =2 oO 11.0 11/16=0.7 0.7/0.7=1 Thus C,H,C1.0 is the empirical formula of the compound 13. A well-known antibiotic penicillin, contains C 57.49 %, H 5.39 %, N 8395, S 958 %, the remainder being oxygen. Given that penicillin contains one atom of sulphur per molecule, cal- culate the molecular formula of the antibiotic. Solution % C =57.49 %H=539 %N=839 % S= 958 % 0 = 100 - (57.49 + 5.39 + 8.39 + 9.58) = 19.15 Empirical formula1.8 ™ Mole Concept and Stoichiometry Element % — Relativeno. Simplest. of atoms Ratio c 57.49 $7.49/12=4.79 16 H 539 539/1=539 18 N 839 839/14=0599 2 s 9.58 958/32=0299 1 ° 19.15 19.15/16=1.196 4 pirical formula is C,,H,,[Link], As the given antibiotic contains only one atom of sul- phur per molecule. The calculated empirical formula C,,H1,.[Link], contains only one atom of sulphur. Hence the same is the molecular formula of the antibiotic. 14. Acompound has molar mass of 147 g Itcontains 49% C and 2.72 % H. On Carius estimation, 2.561 mg of the compound gave 5 mg of AgCl Find the empirical and molecular formula Solution Element % Atomic ratio Simplest Ratio c 49 49/12=4.1 3 H 272 272=272 2 (35.5/143.5) x 5 x 100 a 2381 =479 479/355=134 1 CJH,Clis the empirical formula n= 147/73.5=2 ‘The molecular formula is C,H,Cl, 15. Methyl orange, an acid-base indicator, is the sodium salt of an acid that contains C, H,N, 8 and O, Quantitative analysis gave 51.4.% C, 4.3 % H, 12.8% N, 9.8% Sand 7.0% Na. What is the empirical formula of methyl orange? Solution %C=514 %H=43 %N=128 %S=98 % Na=7.0 %O= 147 Element % Relative no. ‘Simplest of atoms Ratio c sl4 51.412 = 4.28 14 H 43 43/1 =43 14 N 28 284-0914 3 s 98 9.8/32 = 0.306 1 Na 70 7/23 = 0.304 1 0 47 1476=0918 3 So empirical formula is C,H, N,SO\Na Expression of Concentration of Solution ‘The solution whose concentration is exactly known is referred as standard solution and such solutions are prepared in volumetric or standard flask Concentration Itis the amount of solute present in one litre of solu- tion. It is denoted by C or S. _ Weight of solute in gram Cor'S=—~"Votume in litre C=NxE Here N= normality E=[Link] Molarity It is the number of moles or gram moles of sol- ute dissolved per litre of the solution. Molarity is denoted by *M’ = Welt of solute in gram Molar mass volume in hitre @ When molarity of a solution is one, it is called a molar solution. and when it is 0.1, solution is called decimolar solution.Mole Concept and Stoichiometry = 1.9 = Molarity depends upon temperature and its unit ismol/ltre M,V,=MY, = On dilution water added = -V, \ m= When the solution of two different substances react together then MY, _ MY. 7 7 Here M, V, n are molarity, volume and number of molecules taking part in a reaction respectively. = When a mixture of different solutions having dif- ferent concentrations are taken the molarity of the mixture is calculated as follows: M= M,V,+M,V, V+ Vy 0. m= When density and % by weight of a substance in a solution are given molarity is find as follows: Molality It is the number of moles or gram moles of solute dissolved per kilogram of the solvent. It is denoted by ‘m’ ____ Weight of solute in gram ™* Molar mass * wt. of solvent in Kg = If molality is one solution, it is called molal solution. = One molal solution is less than one molar solution, = Molality is preferred over molarity during exper- iments as molality is temperature independent while molarity is temperature dependent. Normality Itis the number of gram equivalents of solute present in one litre of the solution and it is denoted by °N’ Weight of solute in gram Equivalent mass = volume in litre = When normality of a solution is one, the solution is called normal solution and when it is 0.1, the solution is called deci-normal solution Normality Equation N,V, =N,V, = Volume of water added = V,- V, Here V, = volume after dilution V, = volume before dilution = When density and % by weight of a substance in solution are given normality is find as follows: % by weight = d « 10 Equivalent weight Here d = density of solution = When a mixture of different solutions having different concentrations are taken the normal- ity of the mixture is calculated as follows NV, +N,Y, V,FV, w In case of acid base neutralization the normality of the resulting solution N,V,-N,V, i 2 N=—-VFV,_ = To find weight of substance _ NEV W= ooo Relation between Normality and Molarity N « Eq wt. = molarity x molar mass N= molarity x valency N= molarity « number of H’ or OH ion. Mole fraction It is the ratio of moles of one component to the total number of moles present in the solution. It is expressed by X for example, for @ binary solution two component A and B1.10 m Mole Concept and Stoichiometry a, Mole fraction of solute (X,) ==> i or x% Here n,n, represent moles of solvent and solute respectively, Mole fraction does not depend upon temperature as both solute and solvent are expressed by weight. Illustrations 16. Calculate the volume of water to be added to a 100 ml of SN solution to make it 0.01 N. Solution According to normality equation, N,V,=N,V, 0.01 x V,=5* 100 =5%100_ V1 =" Qo = 50000 ml So volume of water to be added = 50000 - 100 = 49900 ml 9.91 17. 10 ml of 0.02 M KMnO, is required to oxi- dize 20 ml of oxalic acid of certain strength. 25 ml of the same oxalic acid is required to neutralize 20 ml of NaOH of unknown strength. Find the amount of NaOH in a litre of the solution (Molecular weight of NaOH = 40) Solution In acidic medium I MKMnO, =5NKMn0, 0.02 M KMn0, = 0.1 NKMnO, According to normality equation, N, V, (KMnO,) = N,V, (Oxalic acid) Ol *10=N, 20 n, = 1054 = 0.05 N Again N, V, (Oxalic acid) = N, V, (NaOH) 0.05 x 25 = N, «20 N, = 295% 25. - 0.0625 N As S=NxE So $=0.0625 « 40=25 gL* 18. The formula weight of an acid is 82.0 100 cm’ of a solution of this acid containing 39.0 g of the acid per litre were completely neu- tralized by 95.0 em’ of aqueous NaOH con- taining 40.0 g of NaOH per litre. What is the basicity of the acid? =. 39 Solution Normality of acid = inet 1000 1000 ‘Now, Mew. of acid = Meq. of NaOH 39n “2 * 100 =40 , = Normality of NaOH = 4 1 1x95 Son=2; Hence here acid is dibasic. 19, What volume at NTP of ammonia gas will be required to be passed into 30 ml of H,SO,solu- tion bring down the acid normality to 0.2 N? Solution Meq. of original H,SO, = 30 x 1 =30 Meq, of H,SO, after passing NH, = 30 « 0.20= 6 Meg, of H,SO, lost = 30-6 = 24 Meg, of NH, passed = Meg, of H,SO, lost w Ty x 1000 = 24 Wy, 70-408 Volume of NH, at STP = 2245-408 = 05376 litre = 537.6 ml 20. What volume of a solution of hydrochloric acid containing 73 g of acid litre would suffice forthe exact neutralization of sodium hydroxide obtained by allowing 0.46 g of metallic sodium to act upon water? Solution Na +H,0 > NaOH + 4H, NaOH + HCI —+ NaC] + H,0 ‘Thus, meq, of Na = Meg. of NaOH formed = Meq. of HCI used 0.46 = Bs 23, Sage (Meg, of HCI =N x V) =10ml Limiting Reagent When two reagents or reactants react to give various product then the number of moles of product form according to the reagent or reactant which is com- pletely consumed during the reaction. The reagent or reactant which is completely consumed during the reaction is called limiting reagent that is, the reagent which gives the least number of moles of the product is called limiting reagent Illustrations 21, 2 gH, reacts with 10 g O, to form water. How much water is formed? Solution Hydrogen reacts with oxygen as follows: 2H, +0, 2H,0 I moles Number of moles of H, ‘Number of moles of O, = 3 = 0.3125 moles As 2 moles of H, reacts with 1 mole of O, to form 2 moles of H,O so, for 1 mole of H, only 0.3125 moles of ©, is present. Thus O, is the limit- ing reagent here. As | mole of O, gives 2 moles of H,O. So 03125 mole of ©, gives } « 0.3125 = 0.625 moles of HO ‘Weight of H,O formed = Moles * Mol, weight = 0.625 « 18 = 11.25 gH,0 Mole Conce ft and Stoichiometry ™ 1.11 Chemical Equations and Numerical Calculations = A balanced chemical reaction represents a stoi- chiometric equation. = Ina stoichiometric equation, the coefficient of reactants and products represents their stoichio- metric amounts. = The reactant which is completely used dur- ing an irreversible reaction is called limiting reagent while the reactant left is called excess reagent. For example, if 20 g of calcium is burnt in 32 gof O, then Ca is limiting reagent while O, is excess reagent = Stoichiometric calculations help in finding whether the production of a particular substance is economically cheap or not = These stoichiometric calculations are of follow- ing four types (a) Calculations based on weight: weight rela- tionship (b) Calculations based on weight: volume rela- tionships. (c) Calculations based on volume: volume relationships (@) Calculations based on weight: volume — energy relationships = If the amount of the reactant in a particular reac- tion is known, then the amount of the other sub- stance needed in the reaction or the amount of the product formed in the reaction can be found out = For stoichiometric calculations, the following steps must be considered: (a) A balanced chemical equation using chemi- cal formulas of reactants and products must be written. (b) Here the coefficients of balanced chemical equation provide the mole ratio of the reac- tants and products (© This mole ratio is convertible into weight — Weight ratio (w/W), weight —volume (W/V) ratio ‘or volume volume (v/V) ratio, These are called percentage by weight, percentage by volume and percentage by strength respectively,1.12 m Mole Concept and Stoichiometry Gravimetric Analysis It is an analytical technique based on the measure- ments of mass of solid substances or the volume of the ‘gaseous species. It is also divided into three categories: (i) Mass-Mass (weight-weight) relation Gi), Mass-Volume relation Gi) Volume-Volume relation (i) Problems Involving Mass—Mass or Weight-Weight Relationship This relationship relates the mass of a reactant or prod- ‘uct with the mass of another reactant or product. For solving such problems, one should proceed according to the following instructions given below: w First, write down the balanced equation to repre~ sent the chemical change. = Now write the number of moles below the formula of the reactants and produet. We must also write the relative weights of the reactants and products (which are calculated from the respective molecu- lar formula) below the respective formula. = Finally, apply the unitary method to calculate the unknown factor(n or s) Illustrations 22. Find weight of iron which will be converted into its oxide by the action of 18 g of steam on it. Solution 3Fe +4H,0 + Fe,0, + 4H, 3x56 4x18 AS 72 ype of Fe oxidized = 168 g So by 18 g 168 « 18 = 18518 = 72g 23. 0.9031 g of NaCl and KCI on reaction with H,SO, gave 1.0784 g of a mixture of Na,SO, and K,SO, Find the percentage composition of the compound. Solution ForX g Naci =X For (0.9031 -X) gKCI= gam x) thats, 173% +774 (0.9031 —X)= 10784 g On solving, we get X= 0.518 57.36% 42.64% Percentage of NaCl = Percentage of KCI = 24, ‘The mineral haematite is Fe,O,. Hematite ore contain unwanted material called gangue in addition of Fe,O,, If 5.0 kg of ore contains 2.78 kg of Fe, what per cent of ore is Fe,0,? Solution 2Fe = 2x5585g 159.78 As 2 = 55.85 g Fe is present in 159.7 g Fe,O, Fe,0. So 2.78 kg Fe is present in _ 159.7 g 2.78 kg 2% S585 g =3.97 kg Fe,0, As 5 kg ore contains = 3.97 kg Fe,0, So 100 kg ore contains = 227100 =79.4 kg FeO, ‘Thus % of Fe,O, in ore=79.4 % 25. 0.256 g sample of iron alloy (a mixture of iron with other elements) was dissolved in hydrochlo- ric acid to give a solution of Fe ion. This solu- tion titrated to the end point with 35.6 ml of 0.1 N KMnO,, which oxidized Fe* to Fe”. What is the mass percentage of iron in the mixture? Solution Reaction of MnO, and Fe* in acidic medium is as follows: MnO, + 8H* + SFe* — Mn* + 4H,O + 5Fe* So MnO, = 5Fe* or 5000 ml. N KMnO, = 5 * 558 gof Fe 35.6 mL. of 0.1 NKMnO, = 5x 55.8 35.6% 0.1 3000 =02gFe As 0.256 g alloy contains = 0.2 g Fe02 100 So 100 g iron alloy contains = 95 5 = 78.125 % (ii) Problems Involving Mass-Volume or Weight-Volume Relationship ‘This relationship relates the mass of a reactant or product with the volume of another gaseous reac- tant o product involved in a chemical reaction For example, Weight of a solid substance can be compared with the volume of gases with the help of the fact that 1 mole or | gram molecule of a gas occupies 22.4 litres or 22400 cc. at NTP. So in brief, the weight-volume relationship can be represented as follows: Ca + 2HCI + CaCl, + H, By mole 1 2 1 1 By amu 40 73 13 2 Bygmwt 40g 73g 13g 2g Bywt 40g 73g 3g 224 or vol litat NIP. For solving such problems one should proceed according to the following instructions given below @ First, write down the relevant balanced chemical equation (s). = Now write the weights of various solid reactants and products m Gases are normally expressed in terms of vol- umes In case the volume of the gas is measured at the room temperature and pressure (that is, any condition other than NTP), convert it into N.T.P. by applying gas laws. ‘The volume of a gas at any temperature and pres- sure can be converted into its weight an vice versa by using this relation, PV=(g/M) «RT Here g is weight of gas, M is molecular weight of gas and R is gas constant Finally, calculate the unknown factor (n or s) by unitary method, Mole Concept and Stoichiometry ™ 1.13 REMEMBER , ‘One should not forget that if other conditions Illustrations 26. A mixture of aluminium and zine weighing 1.67 grams was completely dissolved in acid and the evolved 1.69 litres of hydrogen gas measured at 273 K and one atmosphere pressure. What was the mass of aluminium in the original mixture? Solution [ct the massof aluminium in the sample be ‘A’ g, The mass of Zn =(1.67—A) g The volume of H, at N.T-P. given by Al =3*224xA 2x27 The volume of H, at NTP given by Zn = (167—A) 22.4 | 64 3x224xA sa CO 142.2 « A= 176.26 248 g 27. In a titration experiment, 23.05 ml of 0.100 N NaOH was required to neutralize 10.00 ml of a solution of H,SO, of unknown strength. What was the normality of the acid solution? Solution In a tiation using NaOH and H,SO, Meq of NaOH = Meq of H,SO, ‘The meq, of NaOH used in the titration 23.05 ml NaOH « 0 100 SAO =231 meq, NaOH ‘The normality of the H,SO, solution 2.32 meq H,S0, meq. 1,50, FROORITESO. 028 TSO =0231NH1.14 m Mole Concept and Stoichiometry 28. A 0311 g sample of crude NaOH when dis- solved in water required 46.1 ml of 0.122 N H,SO, to neutralize the NaOH in the sample Calculate the per cent of NaOH in the sample Solution Ina titration using NaOH and [Link], Meq of NaOH = meq. of H,SO, ‘The meq of H,SO, meq H,SO, mi aolatlon = 5.62. meq H,SO, 0.122 * 46.1 ml solution The 5.62 meq, of NaOH . g NaOH 5.62: meq NaOH * 0.040 =e NeOHT - = 0.225 g NaOH The per cent of NaOH in the sample is as follows: 0.225 g NaOH O31T g sample * 100= 72.3% NaOH 29. A volume of 22.5 ml of 2.50 N NaOH was required to neutralize 10.5 ml of a solution of H,SO, of unknown strength. The density of the H,S0, solution was 1.16 g perml. Calculate the per cent by weight of H,SO, in the solution Solution tn a titration using NaOH and 1,50, Meg, of NaOH = meq, of H,SO, The meq, of NaOH: 2.50 BELNO} 22.5 ml solution = 56.3 meq NaOH The 56.3 meq. of H,SO, 56.3 meq, H,S0, x 0.0491 EHO E neq =276gHSO, ‘The weight of the 10.5 ml of H,SO, ge 10,5 ml « 1.16 77-1222 The per cent H,SO, is 2.76 gH,SO, 12.2 g solution * !° = 22.6% H,SO, by weight 30. If required 336 ml of a 0.100 NK,Cr,0, solu- tion to oxidize the Fe" to Fe” in 21.6 ml of a solution of FeSO, of unknown strength Solution The equation is as follows: Cr,0,* + 14 HY +6 Fe* 1.00 mole 6.00 moles 600 geqwt 6.00. g-eqwt 2Cr* + 6Fe* + THO According to this equation, 1.00 g-eq wt of Fe™* ion will originate from 1.00 g-eq wt of FeSO,, we get meq, of Cr,0>= meq, of Fe* = meq, of FeSO, meq, of Cr,0,* is: meq Cr,0? 0.100 “ST solution * 33.6 ml solution = 3.36 meq, Cr,0,? ‘The normality of the FeSO, solution is 3.36 meq FeSO, 21.6 ml solution As FeSO, solution is 0.156 N with respect to Fe* ion, and the number of mg Fe per ml is as follows: 0.156 N FeSO, _mgFe™ 0.156 meq. Fe asta * 5352 ee ~871 st goluion 31. What should be the weight of NaNO, to make 50 ml of an aqueous solution so that it contains 70 mg Na* ml"? Solution Molecular mass of NaNO, = 23+ 14 +3 * 16 = 85g mol ‘As 23 mg Na is present in 85 mg of NaNO, 85.« 70 3 = 258.7 mg NaNO, So 70 mg Na is present inAs | ml solution contains 258.7 mg NaNO, ‘So 50 ml solution contains ___258.7 mg x 50 ml ~ tml = 13935 mg = 13.935 ¢ (iii) Problems Based on Volume-Volume Relationship Thisrelationship relates the volume of gaseous reactant or product with the volume of another gaseous reactant orproduct involved in a chemical reaction, For solving such problems, one should proceed according to the following instructions given below: @ First write down the relevant balanced chemical equation. = Now write down the volume of reactants and prod- ucts below the formula to each reactant and prod- uct using the fact that one gram molecule of every gaseous substance occupies 22.4 litres at [Link]. = If volume of the gas is measured under particular or room temperature, convert it to NLP. with the help of ideal gas equation. = Now use Avogadro's hypothesis “gases under simi- lar eonditions of temperature and pressure contain the same number of molecules”. Thus under similar conditions of temperature and pressure, the volume of reacting gases are proportional to the number of moles of the gases in the balanced equation. Example, N, (g) + 3H,(g) — 2NH,(g) 1 mole 3 moles 2 moles 22.4 lit 3x 224 1it 2x 224 lit I volume 3 volumes 2volumes Ixvolume 3%volume 2.x volumes From the above equation, it is clear that 22.4 litres of N, will react with 322.4 litres of H, to form 2%22.4 litres of NH,. Illustrations 32. Amixture of HCOOH and (COOH), is heated with concentrated H,SO,. The gas produced is collected and on its treatment with KOH Mole Conce ft and Stoichiometry ™ 1.15 solution the volume of the gas decreases by V/éth. Calculate the molar ratio of two acids in the original mixture Solution Reactions HcooH 48%, 17,0 +C0t amole amole H,¢,0, 4, 0+co + co, b mole bmole bmole Total number of moles of CO and CO, =atb+ +2b Total number of moles of CO, =b So Mole fraction of CO, absorbed in KOH -_> a+2b bil a+2b 6 a=4b Thus ratio of HCOOH and H,C,O, is 4: 1 33. A gas mixture of 3 litre of produce (C,H,) and butane (CH,,) on complete combustion at 25°C produced 10 litre CO,. Find out the composi- tion of gas mixture Solution C,H,+50, + 3CO, + 4H,0 (1) C,H, + 13/2 0, + 4CO, + 5H,0 () Supposelitre of C,H, and y litre of C,H, are pres- ent in the mixture. So xty=3 As volume of CO, formed = 10 = CO, formed by C,H, + CO, formed by CH, 10=3x+4b am rcenenifif Solving Eqs. 1. and 2 n-Factor or Valence Factor It is very important for both redox reactions and non-redox reactions by which we can obtain follow- ing informations: