Chapter 3 Stoichiometry Chemical stoichiometry: the study of the quantities of the materials consumed and produced in chemical reactions 3.1 Atomic Masses The modern system for atomic masses is based on 12C as the standard. In this system, C is assigned a mass of exactly 12 atomic mass units. • The unit of mass is the atomic mass unit (amu) • one amu is defined as 1/12 the mass of an atom of carbon with 6 protons and 6 neutrons in its nucleus 1 amu = 1.6605 x 10-24 g 6.022× 1023 amu = 1 g (exactly) The most accurate method available today for comparing the masses of atoms is the mass spectrometer. Ratio of the mass of 12C and mass of 13C is 1.0836129, therefore since the mass of 12C is assigned as exactly 12 amu, the mass of a 13C atom is: (12 amu) X (1.0836129) = 13.003355 amu 1 Why the atomic mass of carbon is listed in periodic tables not equal to exactly 12? Isotopes!!!! 12 C, 13C & 14C Because natural carbon is a mixture of isotopes, the atomic mass listed is the average value reflecting the natural abundance of the three isotopes. It is calculated as follows: 12 C has a natural abundance of 98.89% and 13C an abundance of 1.11%. 14C is negligibly small at this level of precision. 98.89% of 12C (12 amu) + 1.11 % of 13C (13.0034) = 0.9889 x 12 amu + 0.0111 x 13.0034 = 12.01 amu Average atomic mass = Σ (mass of isotope × relative abundance) 3.2 The Mole (mol) • • a mole of any substance is that quantity which contains as many atoms, molecules, or ions as are in exactly 12 g of pure carbon-12 a mole, whether it is a mole of iron atoms, a mole of methane molecules, or a mole of sodium ions, always contains the same number of formula units 2 • • • • the number of formula units in a mole is known as Avogadro’s number Avogadro’s number has been measured experimentally its value is 6.02214199 x 1023 formula units (atoms, ions or molecules) per mole The mole therefore is the molecular weight of a substance (atom, ion or molecule) in grams. Formula Weight • Formula weight: the sum of the atomic weights in atomic mass units (amu) of all atoms in a compound’s formula Ionic Comp ou nds Sod ium chlorid e (N aCl) 23.0 amu N a + 35.5 amu Cl = 58.5 amu Nickel(II) ch loride h yd rate 58.7 amu N i + 2(35.5 amu Cl) + 12(1.0) amu H) + 6(12.0 amu O) = 237.7 amu (N iCl 2• 6H 2O) Molecu lar Comp ou nds Water (H 2O) Aspirin (C 9H 8 O 4) 2(1.0 amu H) + 16.0 amu O = 18.0 amu 9(12.0 amu C) + 8(1.0 amu H) + 4(16.0 amu O) = 180.0 = amu 3 3.3 Molar mass: the formula weight of a substance expressed in grams (the mass in grams of one mole of a pure substance) • Glucose, C6H12O6 • Molecular or formula weight: 180 amu • molar mass: 180 g/mol • one mole of glucose has a mass of 180 g • Urea, (NH2)2CO • Molecular or formula weight 60.0 amu • molar mass: 60.0 g/mol • one mole of urea has a mass of 60.0 g • We can use molar mass to convert from grams to moles, and from moles to grams You are given one of these and asked to find the other Grams of A Moles of A Use molar mass (g/mol) as the conversion factor 4 calculate the number of moles of water in 36.0 g water 36.0 g H 2O x 1 mol H2 O 18.0 g H 2O = 2.00 mol H2 O Grams to Moles • Calculate the number of moles of sodium ions, Na+, in 5.63 g of sodium sulfate, Na2SO4 • first we find how many moles of sodium sulfate are present in 5.63 g of sodium sulfate 5 • the formula weight of Na2SO4 is 2(23.0) + 32.1 + 4(16.0) = 142.1 amu • therefore, 1 mol of Na2SO4 = 142.1 g Na2SO4 5.63 g Na2 SO 4 x 1 mol Na2SO 4 142.1 g Na2 SO 4 = 0.0396 mol Na2SO 4 • the formula Na2SO4 tells us there are two moles of Na+ ions per mole of Na2SO4 0.0396 mol Na2 SO 4 + 2 mol Na x 1 mol Na2SO 4 = 0.0792 mol Na+ 6 Grams to Molecules • A tablet of aspirin, C9H8O4, contains 0.360 g of aspirin. How many aspirin molecules is this? • first we find how many mol of aspirin are in 0.360 g 0.360 g aspirin x 1 mol aspirin 180.0 g aspirin = 0.00200 mol as pirin each mole of aspirin contains 6.02 x 1023 molecules • the number of molecules of aspirin in the tablet is 0.00200 mole x 6.02 x 1023 molecules = 1.20 x 1021 molecules mole 7 3.4 Percent Composition of Compounds There are two common ways of describing the composition of a compound: in terms of the numbers of its constituent atoms and in terms of the mass percentages of its elements. Percent composition is the atomic weight for each element divided by the formula weight of the compound multiplied by 100: (textbook examples) % Element Atoms of Element AW FW of Compound 100 3.5 Determining the Formula of a Compound The formula of a compound can be obtained by elemental combustion analysis (CHN analysis): 8 The result of such an analysis provides the mass of each type of element in the compound, which can be used to determine the mass percent of each element and from this information the formula of a compound can be deduced. (example on page 96) After calculating percentages, work with a 100 g sample of the compound. 38.67% Carbon by mass means 38.67 g of carbon. 16.22% Hydrogen by mass implies 16.22 g of hydrogen 45.11% Nitrogen by mass translates to 45.11 g of nitrogen Now calculate the number of C atoms in 38.67 g of C, etc… C: 38.67 g C X 1 mol C/12.01 g/mol C = 3.220 mol of C H: 16.22 g H X 1 mol H/1.008 g/mol H = 16.09 mol H N: 45.11 g N X 1 mol of N/14.01 g/mol N = 3.219 molN Thus 100 g of this compound contain 3.220 mol of C atoms, 16.09 mol of H atoms and 3.219 mol of N atoms. The smallest whole-number ratio of atoms in this compound is obtained by dividing the three numbers above by the smallest of the three. 9 C: 3.220/3.219 = approx 1 H: 16.09/3.219 = approx 5 N: 3.219/3.219 = 1 Therefore the Empirical Formula (a formula providing the smallest whole-number ratio of elements) for the compound is: C1H5N1 or CH5N. The compound could be CH5N or C2H10N2 etc… To obtain the molecular formula we need to know the molar mass of the compound. Suppose the molar mass of our compound is 31.06 g/mole. How do we determine the molecular formula? The molecular formula is always a whole-number multiple of the empirical formula. The empirical formula mass of CH5N is given as 31.06 g/mol. Therefore what is the molecular formula? 10 3.6 Chemical equations A chemical change involves a reorganization of the atoms in one or more substances. Remember that mass (or atoms in this case) is neither created nor destroyed. The following chemical equation tells us that propane gas and oxygen gas (reactants) react to form carbon dioxide gas and water vapor (products) 11 C3 H8 ( g) + O2 (g) CO2 (g) + H2 O( g) Propane Carbon dioxid e Oxygen Water But while it tells us what the reactants and products are and the physical state (s, l, g or aq) of each, it is incomplete because it is not balanced. A chemical equation for a reaction must provide all the info about the nature of reactants and products, the relative numbers of each and the physical state of each. 2Na (s) + 2H2O (l) 2NaOH (aq) + H2 (g) Stoichiometric coefficients: numbers in front of chemical formulas; provide ratio (relative numbers) of reactants and products in a chemical equation. 12 3.7 Balancing Chemical Equations To balance a chemical equation (more than one method), begin with atoms that appear only in one compound on the left and one on the right; in this case, begin with carbon (C) which occurs in C3H8 and CO2 C3 H8 (g) + O2 (g) 3CO2( g) + H2 O(g) now balance hydrogens, which occur in C3H8 and H2O C3 H8 (g) + O2 (g) 3CO2( g) + 4H2 O(g) if an atom occurs as a free element, as for example Mg or O2, balance this element last; in this case O2 C3 H8 (g) + 5O2 ( g) 3CO2 (g) + 4H2 O( g) 13 Practice problems: balance these equations Ca( OH) 2 ( s) + HCl( g) Calcium hydroxide CO2 ( g) + H2 O(l) CaCl2 (s) + H2 O( l) Calcium chlorid e photosynthes is C6 H1 2 O6 (aq) + O2 (g) Glucose C4 H1 0 ( g) + O2 (g) Butane CO2 (g) + H2 O(g) 3.8 Stoichiometric Calculations: Reactants & Products Amounts of Stoichiometry: the study of mass relationships in chemical reactions 14 An overview of the types of calculations under study You are given one of these Grams of A And asked to find one of these Moles of A From grams to moles, use molar mass (g/mol) as a conversion factor C3 H8 (g) + 5O2 ( g) Moles of B Grams of B From moles to moles, From moles to grams, use the coefficients in use molar mass (g/mol) the balanced equation as a conversion factor as a conversion factor 3CO2 (g) + 4H2 O( g) What mass of Oxygen will react with 96.1 g of Propane? The above equation tells us that 1 mole of propane reacts with 5 moles of oxygen to produce 3 moles of carbon dioxide and 4 moles of water. We must be able to convert between masses and moles of substances. We ask ourselves how many moles of propane are present in 96.1 g of propane. The molar mass of propane is 44.1 g/mole: 15 The number of moles of propane in 96.1 g is: 96.1 g propane X 1 mol propane/44.1 g propane = 2.18 mol propane Now keep in mind that each mole of propane reacts with five mole of oxygen (reaction stoichiometry). Therefore construct a mole ratio: 5mol oxygen/1 mol propane Multiplying the number of moles of propane available with this conversion factor gives the number of moles of oxygen required. 2.18 mol propane X 5 mol oxygen/1 mol propane = 10.9 mol oxygen 10.9 mol oxygen X 32.0 g oxygen/1 mol oxygen = 349 g oxygen Problem: how many grams of nitrogen, N2, are required to produce 7.50 g of ammonia, NH3 N2 (g) + 3H2 (g) 2NH3 ( g) 16 first find how many moles of NH3 are in 7.50 g of NH3 7.50 g N H 3 x 1 mol N H 3 17.0 g N H 3 = mol NH 3 next find how many moles of N2 are required to produce this many moles of NH3 7.50 g N H 3 x 1 mol N H 3 17.0 g N H 3 x 1 mol N2 2 mol N H 3 = mol N 2 finally convert moles of N2 to grams of N2 and now do the math 7.50 g NH 3 x 1 mol NH 3 17.0 g NH 3 x 1 mol N2 2 mol NH 3 x 28.0 g N 2 1 mol N2 = 6.18 g N 2 17 How many grams each of CO2 and NH3 are produced from 0.83 mol of urea? ( NH2 ) 2 CO(aq) + H2 O Urea urease 2NH3 (aq) + CO2 (g) 3.9 Calculations Involving a Limiting Reactant (reagent). In a chemical reaction, reagents are mixed together in stoichiometric quantities (exact amounts) so that all reagents are consumed at the same time and no unreacted substance is left without reacting. Consider the formation of water from its two constituent elements. 18 Once hydrogen is consumed, the reaction stops, i.e. production of water stops although there is still oxygen left to react. In this particular case the amount of hydrogen limits the production of water, which brings us to the concept of limiting reagent (reactant). Limiting reagent: the reagent that is used up first in a chemical reaction. The reaction stops after the limiting reagent is consumed although other reagent(s) are still available. Consider this reaction of N2 and O2 N2 (g) + O2 (g) before reaction (moles) 5.0 after reaction (moles) 4.0 1.0 0 2 NO( g) 0 2.0 In this experiment, there is only enough O2 to react with 1.0 mole of N2 O2 is used up first; it is the limiting reagent. 4.0 Moles of N2 remain unreacted. (textbook gives the example of nitrogen and hydrogen reacting to produce ammonia) 19 Practice Problem Suppose 12 g of carbon is mixed with 64 g of oxygen and the following reaction takes place C(s) + O2 ( g) CO2 ( g) Complete the following table. Which is the limiting reagent? C before reaction (g) 12 g + O2 CO2 64 g 0 before reaction (mol) after reaction (mol) after reaction (g) Theoretical Yields The amount of product predicted from stoichiometry taking into account Limiting reagents is called the theoretical yield (the amount of product formed when the limiting reagent is completely consumed). 20 The percent yield relates the actual yield (amount of material recovered in the laboratory) to the theoretical Actual yield % Yield 100 Theoretica l yield yield: Practice problem: Suppose we react 32.0 g of methanol with excess carbon monoxide and get 58.7 g of acetic acid CH3 OH + CO before reaction (g) 32.0 before reaction (mol) th eoretical yield (mol) th eoretical yield (g) actual yield (g) percent yield (%) excess CH3 COOH 0 58.7 Text book examples on pages 117 & 119 21 22