Section 1B Section 1B The Mole Concept & Chemical Calculation / Page 1 The Mole Concept & Chemical Calculation Mole and Avogadro Number Chemists developed a unit to represent the number of particles in a sample. This unit is the mole (Latin, means 'pile'). of The mole was defined as the amount of substances which contains 12 particles as in 12 g of 6 C . the same number 23 Experiments show that 12 g of carbon has 6.02 x 10 atoms. This number is known as Avogadro number (honoring an Italian chemist, Amadeo Avogadro). The Mass of One Mole of a Substance The weight of 1 mole of substance (molar mass) always corresponds to its formula express in gram units. mass In the definition for mole, the particles may be atoms, molecules, ions, electrons or other particles. no. Example 1 of mole = no. of pa r ticles 3 A no. 6.02 x 1023 5 cm spoon can hold 23 1.67 x10 of mole = Mass Molar mass molecules of water. a) What is the number of moles of water molecules in the spoon? b) What is the mass of water in the spoon? Example 2 1 mole of helium atom weighs ______ g and contains ___________________ helium atoms, i.e. ________ mole of helium atoms. 1 mole of nitrogen molecules weighs moles nitrogen atoms _________ g and contains ____________ 1 mole of AlCl3 weighs _______ g, contains _______ mole of aluminium ions and ______ moles of chloride ions. _____________________________________________________________________________________ . 1 What is the mass of 2.5 moles of potassium atoms? 2 What is the number of nitrogen atoms in 0.5 mole of nitrogen gas, N 2? 3 The number of sodium atoms in 4.6 g of sodium metal is 4 Calculate the mass of a] 3.0 mole of neon atoms b] 0.10 mole of lithium atoms Section 1B The Mole Concept & Chemical Calculation / Page 2 The Molar Volume The volume occupied by one mole of a substance is called the molar volume. For gases, experiments show that at the same temperature and pressure, molar volumes of all gases are roughly equal. Gas Formula Molecular mass Hydrogen Density -3 (g dm ) 0.083 Helium 0.166 Ammonia 0.706 Oxygen 1.333 Carbon dioxide Molar volume 3 (dm ) 1.811 Chlorine 2.994 i.e. The molar volume of any gas is approximately _______ at 25oC 。 and 1 atmospheric pressure (r.t.p.) The molar volume of any gas is __________ at standard teperature and pressure (s.t.p.) Avogadro's Law Avogadro's law states that equal volumes of all gases at the same pressure contains the same number of molecules. For example, 24 dm and of any gases at r.t.p. contain 1 mole of molecules. 3 Example 1 . 3 temperature How many moles of carbon dioxide is present in 5.58 dm of this gas at s.t.p. ? 5 What is the number of moles of molecules in 6 dm 6 1.4 g of a gas has a volume of 1.2 dm of the gas. no. of mole = 3 3 of oxygen gas? at r.t.p. Calculate the relative molecular mass Vol ume Mola r v ol ume The Ideal Gas Equation In 1662, Robert Boyle had discovered that the volume of a fixed mass of gas is inversely proportional to its pressure, provided the temperature remains constant. This is known as Boyle's Law, Which can be expressed as: PV = constant or V 1 P In1787, Charles showed that the volume of a fixed mass of gas is directly proportional to its absolute temperature (0oC = 273K), provided the pressure remains constant. This is called the Charles's Law which can be expressed as: P V = constant or V T Section 1B The Mole Concept & Chemical Calculation / Page 3 In 1811, the Italian scientist Avogadro put forward his theory which stated that equal volumes(V) of gases, under the same conditions of temperature and pressure, contain equal numbers(n) of molecules. i.e. V n By considering the above 3 Laws, we can obtain the following result: V 1 P V PV and = nT P nRT V T and V PV nT n (The Ideal Gas Equation) R = Universal gas constant Determination of relative molecular masses The Ideal Gas Equation provides the basis for the determination of the relative molecular mass of a gas or low boiling liquid. By finding the volume of the gas (or vapour formed from a known mass of a liquid), at a known temperature and pressure, the relative molecular mass of the compound can be calculated. The apparatus and experimental procedure used to determine the relative molecular mass of a volatile substance (e.g. propanone) is given below: steam i n graduated gas syri nge self-seali ng rubber cap hypodermi c syri nge thermometer steam jacket steam and water out Procedure: 1. The apparatus is set up as shown, with a few cm3 of air being deliberately drawn into the gas syringe. This allow for some space for the propanone to vaporise and expand smoothly in the gas syringe. 2. Pass steam through the jacket until the thermometer reading and the volume of air in the syringe reach steady values. Record the temperature and air volume(V1). 3. Rinse the hypodermic syringe with the liquid that is to be investigated. Recharge the 3 hypodermic syringe with about 1 cm of liquid, expel air from the needle by pushing in the plunger gently. Dry the outside of the needle. 4. Inject about 0.2 cm of liquid into the large syringe. The volume of liquid injected needs not to be very accurately noted, since the mass of the liquid injected would be determined by weighing the hypodermic syringe before and after injection. Between the weightings handle the hypodermic syringe as little as possible to reduce loss of liquid by expansion or evaporation. 5. Record the volume(V2) of air plus vapour in the graduated syringe when the reading become steady (this ensures complete vaporization of liquid and the vapour pressure inside is equal to atmospheric pressure outside). Pressure = 1 atm ; Volume of vaporized gas = V2 - V1 3 _____________________________________________________________________________________ Example 1 . 7 Section 1B The Mole Concept & Chemical Calculation / Page 4 3 Calculate the molar mass of B, given that 0.850 g of B occupied 59.5 cm at r.t.p. 0.228 g 86.3 cm of liquid was injected into a gas syringe. The volume of vapour formed was 3 at r.t.p. Calculate the molar mass of the substance. Dalton's Law of Partial Pressure Dalton's law of partial pressure states that the total pressure of a mixture of gases which do not react together chemically is equal to the sum of the pressures that each gas would exert if it occupied the space alone. Ptotal = P1 + P2 + P3 + + Pn Partial pressure of a gas is the pressure that the gas would exert if it alone occupied the whole volume. Mathematically, it can be expressed as follow: Ptotal = Partial pressure , P1 = The magnitude of the partial pressure of a gas is related to the number of mole of that gas present in the container: mole fraction (1) = Partial pressure , P1 = _____________________________________________________________________________________ 5 -2 Example 1: A mixture of gases at a pressure of 1.01 x 10 Nm contains 25% of oxygen. What is the partial pressure of oxygen in the mixture? by volume Section 1B . 8 The Mole Concept & Chemical Calculation A mixture of gases at a pressure 40% N2 ; 35% O2 ; 25% CO2. 4 -2 7.50 x 10 Nm / Page 5 has the volume composition (a) What is the partial pressure of each gas? (b) What will the partial pressures of nitrogen and oxygen be if the carbon dioxide is removed by the introduction of some sodium hydroxide pellets? Faraday and the mole Quantity of Electricity Quantity of electricity (Q) = in coulombs (C) Example 1 : current (I) X in amperes (A) time (t) in seconds (s) A current of 0.25 A passing for 2 minutes. What is the quantity of electricity passed ? The Faraday Unit 1 Faraday = 1 mole of electrons = 96500 coulombs Example 1: Find the quantity of electricity (in faradays) required to liberate + i) 1 mole of Na ii) . 9. 0.5 mole of Fe 2+ Find the quantity of electricity (in faradays) required to liberate 2+ i) 1 mole of Cu ii) 2 moles of Al iii) 2 moles of H2 3+ Section 1B The Mole Concept & Chemical Calculation / Page 6 Faraday's Law of Electrolysis Faraday's First Law The mass (m) of a substance liberated at an electrode during electrolysis is directly proportional to the quantity of elecltricity (Q) passed through the electrolyte. i.e. m Q Faraday's Second Law The quantity of electricity (Q) required to produce a mole of a substance from its ions is proportional to the charge on the ions (Mn+). Q n Example 1: A current of 1.5 A was passing through a solution of silver nitrate for 1.5 hours. What was the mass of silver produced ? Example 2: How many hours will it take for a current of from a solution of copper sulphate ? . 1.5 A to deposit 0.80 g of copper 10. A metal M has a relative atomic mass of 88. When a current of 0.5A was passed for 16 minutes 5 seconds, 0.22 g of M was deposited on the cathode. i) Calculate the number of faradays of electricity needed to liberate 1 mole of atoms. ii) What is the charge carried by an ion of iii) Write an ionic equation for the reaction at the cathode. M M? 11. Whan an aqueous solution of sodium hydroxide is electrolysed using platinum electrodes, the hydroxide ions are discharged at the anode to give oxygen according to the following half-equation: 4 OH- (aq) 2 H2O (l) + O2 (g) + 4 eIf a current of 2.5 A is passed for 15 minutes, i) how many moles of OH- ions are discharged ? ii) how many moles of oxygen (O2) are produced ? iii) what is the volume of this oxygen at r.t.p. ? 3 24 dm ) (molar volume of gases at r.t.p. = Section 1B The Mole Concept & Chemical Calculation / Page 7 12. A metal spoon is electroplated with silver in silver nitrate solution, using a current of 0.5 A for one hour. (relative atomic mass: Ag = 108.0 ; 1 Faraday = 96500 C) i) Draw a labelled diagram showing how this experiment can be carried out in the laboratory. ii) Write an equation for the reaction which occurs at the metal spoon. iii) Calculate the mass of silver deposited on the spoon. Chemical Formulae Chemical formulae can sometimes be predicted from the theoretical argument based on the atomic structure, but basically they are determined experimentally. In order to find the formula of a compound, we should know a] b] what elements are present ; and relative number of each atoms/ions present in the compound. There are several types of formulae which are commonly used. These are: 1. Empirical formula - It is the formula which shows the simplest integral ratio of the relative number of atoms or ions present. (whole number) 2. Molecular formula - It is the formula which shows the actual number of each kind of atom in one molecule of the compound. (This type of formula is only applicable for covalent compounds because only covalent compounds are exist in discrete molecules) Determination of formulae of simple compounds from percentage composition by mass In order to find the formula of a compound, it is first necessary to find the ratio mass of each element in the compound. by After finding the masses of each element, these masses can be converted into moles. The ratio of these mole values gives the empirical formula. Example 1: To find the formula of copper copper oxide oxide excess town gas burning with a small flame Town gas HEAT In performing the above experiment, the following points should be noted: i] It is necessary to pass the town gas for a few seconds before igniting it at the outlet. This is to ensure that all the air inside the tube has been displaced. The gas coming out of the hole is thus pure town gas, which will burn quietly and safely on ignition. ii] iii] Section 1B The Mole Concept & Chemical Calculation / Page 8 Excess town gas has to be burnt away, otherwise it will escape into the laboratory. Town gas is poisonous and may catch fire easily. The solid residue after complete reaction should be allowed to cool with town gas still passing over it. If the town gas supply is stopped at once after the reaction, air will be drawn into the glass tube as it cools, then the hot copper would easily combine with oxygen in the incoming air to form back copper oxide. To prevent this, copper is allowed to cool in an atmosphere of town gas. Specimen results: mass mass mass mass mass mass of of of of of of test tube test tube + copper oxide test tube + copper copper oxide copper in oxide oxygen in oxide (Given: atomic mass of copper = = = = 21.320 g 22.950 g 22.622 g ______ g = ______ g = ______ g = 63.5 ; no. of mole of copper in copper oxide = of Copper(Cu) : Oxygen(O) = 16) = no. of mole of oxygen in copper oxide ratio atomic mass of oxygen = = = ___ : ___ Therefore, the formula of copper oxide is ________________ . Example 2: To determine the empirical crucible formula lid of magnesium oxide pipe-clay triangle magnesium heat Specimen mass mass mass mass mass mass of of of of of of results: crucible + lid crucible + lid + magnesium crucible + lid + magnesium oxide magnesium oxide magnesium oxygen present in the oxide Mg = 20.635 g = 21.555 g = 22.165 g = _____ g = _____ g = _____ g O no. of mole ratio Therefore, the formula of magnesium oxide is _____________ Example 3: A compound has the empirical formula CxHy . On analysis, 1.000 g of the compound is found to contain 0.857 g of carbon. Find values of x and y . C H masses no. of mole = = ratio Empirical formula is ______. Therefore , x = ___ and y = ___. Example 4: Section 1B The Mole Concept & Chemical Calculation / Page 9 A compound X contains 80 % carbon and 20 % hydrogen. Find its empirical formula. Find also its molecular formula if the vapour density of X is 15 . Assume we have _____ g of compound Carbon X. Hydrogen masses no. of mole = = ratio Empirical formula is ______. Vapour density = densit y of t he gas densit y of h yd r ogen = = molar mass of t he gas molar v ol ume molar mass of H gas 2 molar v ol ume = molec ular mass of the gas 2 mass o f t he gas vol ume mass of H gas 2 vol u me mola r gas of t he gas mola r mass of H 2 gas = Molecular mass of X = 2 x V.D. = Let ______ be the molecular formula of X. Molecular formula of X = is _________. 13 A sample of a hydrated compound was analysed and found to contain 2.10 g of cobalt, 1.14 g of sulphur, 2.28 g of oxygen and 4.50 g of water. Calculate its empirical formula. (CoSO4 . 7 H2O) Co S O H2O masses no. of mole = = = = ratio Empirical formula is ___________. (no molecular formula for ionic compound) 14 10.00 g of hydrated barium chloride is heated until all the water is driven off. The mass of anhydrous compound is 8.53 g . Determine the value of x in BaCl 2 . x H2O. (2) 15 Determine the formula of a mineral with the following mass composition: Na = 12.1 % ; Al = 14.2 % ; Si = 22.1 % ; O = 42.1 % ; H 2O = 9.48 %. (Na2Al2Si3O10 . 2 H2O) Section 1B The Mole Concept & Chemical Calculation / Page 10 Calculation based on equations If the balanced equation for one reaction is known, it is possible to calculate the masses of the products if the masses of the reactants are given, or vice versa. The steps in this type of calculation are as follow: a] write down the balanced equation for the reaction b] convert the amounts of given substances into mole quantities (this may not be necessary in case of gases reactions) c] calculate the mole quantities of the required substances using the stoichiometric coefficient given by the equation d] change the mole quantities back into mass or volume as required by the question Example 1: Calculate the volume of hydrogen evolved at r.t.p. when 1.3 g of sodium reacts with excess water. Step 1 Equation Step 2 into Step 3 moles Step 4 into Example 2: no. of moles by equation volume Calculate the mass of magnesium oxide formed when are burnt with excess oxygen. 2.43 g of magnesium Calculation involving gaseous volume In this type of calculation, we must first know a very important fact - the Avogadro's Law. This law states that equal volumes of all gases contain the same number of molecules (if temperature and pressure are the same). Therefore, by applying Avogadro's law, mole ratio of gases can be converted into volume ratio and vice versa. Example 1: Methane, CH4, burns in oxygen to give carbon dioxide and water. If 10 dm 3 of methane burns, calculate : [a] the volume of oxygen required ; [b] the volume of the products formed (measured at room temperature and pressure). Equation : mole by equation volume by Avogadro‘s law Volume Volume Volume Example 2: of of of oxygen products ( products ( = )= ________ ________ ) = ________ Calculate the volume of oxygen required for the complete combustion of 100 3 cm of ethane, C2H6 . What is the volume of carbon dioxide and water formed, assuming all the volumes are measured at room temperature and pressure? Section 1B The Mole Concept & Chemical Calculation / Page 11 Molarity of a Solution Molarity (M) is the number of moles of solute dissolved in 1 dm3 Molarity of a solution(M) of solution. n umber of mole of sol ute (n) vol ume of sol ution in dm3(V) = Number of moles of solute present = Molarity x Volume of solution in dm i.e. n = M x 3 V _____________________________________________________________________________________ 3 Example 1 How many grams of sodium hydroxide are needed to prepare 3 dm of Example 2 How many dm 3 of 0.05 M NaCl can be prepared from 11.7 g 2M of NaOH? NaCl ? _____________________________________________________________________________________ 16 Calculate the molarity of each of the following solutions: 3 a) 4 g of NaOH in 1 dm b) 9.8 g of H2SO4 in 500 cm 3 17 Calculate the mass of solute in each of the following solutions: 3 a) 250 cm of 2M NaOH b) 100 cm 3 of 0.5 M HCl _____________________________________________________________________________________ Calculations in Acid-Base titrations 3 Example 1 20.0 cm of a solution of barium hydroxide, Ba(OH) 2 , of unknown concentration is placed in a conical flask and titrated with a solution of hydrochloric acid, HCl , 3 which has a concentration of 0.06 M . The volume of acid required is 25.0 cm . Calculate the concentration of the barium hydroxide solution. Step 1 Equation Step 2 into Step 3 moles Step 4 into moles by equation concentration (M) Section 1B Example 2 2.65 g The Mole Concept & Chemical Calculation / Page 12 of sodium carbonate (Na 2CO3) were dissolved in water and made up to 250 3 3 3 cm solution. 25.0 cm of this required 20.0 cm of a hydrochloric acid solution for complete reaction. Find the molarity of the hydrochloric acid. Step 1 Equation Step 2 into Step 3 moles Step 4 into moles by equation molarity (M) 3 Example 3. 50.0 cm of 0.50 M nitric acid were added to 1.28 g of a sample of calcium carbonate containing sand as impurity. The excess acid was found to be 3 neutralized by 20.0 cm of 0.40 M sodium hydroxide solution. Find the percentage purity of the calcium carbonate. Step 1 Equation 1 Equation 2 Step 2 into Step 3 moles Step 4 into . moles by equation mass (g) 18 On diluting a sample of ethanoic acid 3 (CH3COOH) five times, it was found 3 that 25 cm of the dilute solution required 30.0 cm of 0.10 M sodium hydroxide solution for complete neutralization. What was the concentration of original -3 acid in mol dm ? (0.60 M) Step 1 Step 2 Step 3 Step 4 19 5.00 g of an impure sample of potassium carbonate (K 2CO3) required 2.00 M hydrochloric acid for complete reaction. What is the percentage purity of the carbonate? Step 1 Step 2 Step 3 Step 4 34.2 cm 3 of (94.4 %) Section 1B 20 8.0 g The Mole Concept & Chemical Calculation / Page 13 of a sample of hydrated sodium carbonate , Na2CO3 . n H2O , are dissolved in 3 water and the solution is made up to 250 cm . Using methyl orange as indicator, 25 3 3 cm of this solution required 28.0 cm of 0.10 M sulphuric acid for complete reaction. Calculate n , the number of molecules of water of crystallization, in the sample of sodium carbonate crystals. (10) Step 1 Step 2 Step 3 Step 4 _____________________________________________________________________________________ Calculations in Redox Titration Example 1 Acidified potassium permanganate solution oxidizes oxalic acid to carbon dioxide and water according to the following equation: 2 MnO4-(aq) + 5 H2C2O4(aq) + + 6 H (aq) 2+ 2 Mn (aq) + 8 H2O(l) 3 + 10 CO2(g) 3 25 cm of 0.20 M oxalic acid solution required 20.0 cm of potassium permanganate solution for complete reaction. Find the molarity of the potassium permanganate solution. Step 2 Step 3 Step 4 . 21 Potassium permengate solution oxidizes iron(II) salt to iron(III) salt according to the following ionic equation: 5 Fe 2+ (aq) + - MnO4 (aq) + + 8 H (aq) 5 Fe 3+ (aq) + Mn 2+ (aq) + 4 H2O (l) 3 1.817 g of potassium permanganate are dissolved in water to give 250.0 cm of aqueous solution. 2.185 g of an iron(II) salt are dissolved in water and the solution 3 3 3 made up to 100 cm . 40.0 cm of this iron(II) salt solution require 25.0 cm of the permanganate solution for complete reaction. (a) What is the molarity of the potassium permanganate solution? (0.046 M) (b) What is the molarity of the (0.1438 M) Fe 2+ ions in the iron(II) salt solution? (c) Section 1B The Mole Concept & Chemical Calculation 2+ Given that 1 mole of the iron(II) salt contains 1 mole of Fe is the molar mass of the iron(II) salt ? (152.0 g) (d) What is the percentage by mass of iron in the salt ? / Page 14 ions, what (36.84%) 3 22 25.0 cm of a solution of potassium permanganate(KMnO4) were added to excess of potassium iodide(KI) solution and the iodine(I 2) liberated was titrated with sodium 3 thiosulphate(Na2S2O3) solution. 25.2 cm of 0.12 M thiosulphate solution were used. Calculate the molarity of the permanganate solution. (0.0242 M) Equation 1: Equation 2: no. of mole of S2O32- no. of mole of I2 formed = no. of mole of I reacted = no. of mole of MnO4- Molarity of - MnO4- used = used = solution = Past Paper 96IIA 2(a) (ii) 95IIA 3(a) (i) (ii) N2 at 0.20 Pa pressure was mixed with 2.0 dm3 of O2 at 0.40 Pa in a 4.0 dm 3 container. Assuming that both N2 and O2 behave ideally, calculate the pressure of the gaseous mixture at 298 K. (2 marks) At 298 K, 1.0 dm3 of Derive an expression for the molar mass M of an ideal gas, in terms of its density d, pressure P, and absolute temperature T. At 98.6 kPa and 300 K, the density of a sample of dry air is 1.146 g dm 3. Assuming that dry air contains only nitrogen and oxygen and behaves ideally, calculate the composition of the sample. (Gas constant, R = 8.31 J K- 1 mol- 1) 94IA (5 marks) 1(d) An aqueous solution of a titanium (Ti) salt was electrolysed by passing a current of 5.00 A for 2.50 hours. As a result, 5.60 g of metallic Ti were deposited at the cathode. Deduce the charge on the Ti ion in the solution. (Given: 1 faraday = 96500 C mol - 1) (3 marks) Section 1B 91IA The Mole Concept & Chemical Calculation / Page 15 2(c) A container holds a gaseous mixture of nitrogen and propane. The pressure in the container at 200 is 4.5 atm. At - 40oC the propane completely condenses and the pressure drops to 1.5 atm. Calculate the mole fraction of propane in the original gaseous mixture. (3 marks) Section 1B Making 96IIA The Mole Concept & Chemical Calculation Scheme 2(a) (ii) PV = nRT 0.2(1) = n N 2 RT and 0.4(2) = n O2 RT Ptotal (4)= ( n N 2 + n O2 )RT = 0.2 + 0.8 =1 Ptotal = 14 = 0.25 Pa 95IIA / Page 16 3(a) (i) (2 marks) PV = nRT 1 2 m where m is the mass of dry air M m PV = (RT) M m M = (RT) PV d = (RT) where d is the density of dry air P n = (ii) Molar = = mass of dry 1 2 1 air 1.146 x 8.31 x 300 98.6 28.98 1 Let mole fraction of N2 be x. 28.02 x + 32.0 (1 - x) = 28.98 1 x = 0.759 Composition 1 of dry air 75.9% N2 and 24.1% O2. (5 marks) 94IA 1(d) i.e. 1 Tin+ + nemole of Ti requires No. of moles of Ti liberated = No. of moles of e- passed n = 91IA Ti produced 2(c) P1V1 = P2V1 = nt(1 - x)RT2 where nt is propane. (2) (1) 0.4663 0.1169 n = = 0.4663 = 3.989 = x e -. 1 1 4 1 (1) number of P2 P1 1.5 473 (1 - x) = ( )( ) = 0.6767 4.5 233 (1 - x) of (3 marks) ntRT1 total moles 5.60 = 1.169 x 10-1 47.90 5.00 x 2.50 x 60 x 60 96500 (2) moles, x is mole fraction T2 = T1 = 0.3233 2 1 (3 marks) of