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Chemistry, The Central Science, 8 or 9 or 10 or 11th edition Theodore L. Brown, H. Eugene LeMay, Jr., and Bruce E. Bursten Dr.Imededdine Arbi Nehdi Chemistry Department, Science College, King Saud University Box 2A93, B5 Stoichiometry © 2009, Prentice-Hall, Inc. Chapter 2 Stoichiometry: Calculations with Chemical Formulas and Equations Dr.Imededdine Arbi Nehdi Chemistry Department, Science College, King Saud University Stoichiometry © 2009, Prentice-Hall, Inc. Chemical Equations Chemical reactions are represented in a concise way by chemical equations. CH4 (g) + 2 O2 (g) CO2 (g) + 2 H2O (g) -The starting substances, called reactants (left side of the equation) - The substances produced in the reaction, called products (appear on the right side of the equation) - The number in front of the chemical formulas are Stoichiometry coefficients. © 2009, Prentice-Hall, Inc. Law of Conservation of Mass (Antoine Lavoisier, 1789) This law states that matter can neither be created nor destroyed; it can only change from one form to another. - According to this Law: during any chemical reaction, the total mass of the reactants or starting materials must equal the mass of the products. - According to this Law :because atoms are neither created nor destroyed in any reaction, a chemical equation must have an equal number of atoms of each element on each side of the narrow. When this condition is met, the equation is said to be balanced. Stoichiometry © 2009, Prentice-Hall, Inc. Subscripts and Coefficients Give Different Information • Subscripts tell the number of atoms of each element in a molecule. Stoichiometry © 2009, Prentice-Hall, Inc. Subscripts and Coefficients Give Different Information • Subscripts tell the number of atoms of each element in a molecule • Coefficients tell the number of molecules. • Subscripts should never be changed in balancing an equation. Stoichiometry © 2009, Prentice-Hall, Inc. Reaction Types Stoichiometry © 2009, Prentice-Hall, Inc. Combination Reactions • In this type of reaction two or more substances react to form one product. • Examples: – 2 Mg (s) + O2 (g) 2 MgO (s) – N2 (g) + 3 H2 (g) 2 NH3 (g) – C3H6 (g) + Br2 (l) C3H6Br2 (l) Stoichiometry © 2009, Prentice-Hall, Inc. Decomposition Reactions • In a decomposition one substance breaks down into two or more substances. • Examples: – CaCO3 (s) CaO (s) + CO2 (g) – 2 KClO3 (s) 2 KCl (s) + O2 (g) – 2 NaN3 (s) 2 Na (s) + 3 N2 (g) Stoichiometry © 2009, Prentice-Hall, Inc. Combustion Reactions • These are generally rapid reactions that produce a flame. • Most often involve hydrocarbons reacting with oxygen in the air. • Examples: – CH4 (g) + 2 O2 (g) CO2 (g) + 2 H2O (g) – C3H8 (g) + 5 O2 (g) 3 CO2 (g) + 4 H2O (g) Stoichiometry © 2009, Prentice-Hall, Inc. Formulas Weights Stoichiometry © 2009, Prentice-Hall, Inc. CH4 (g) + 2 O2 (g) CO2 (g) + 2 H2O (g) • Chemical formulas and chemical equations both are a quantitative significance; the subscripts in formulas and the coefficients in equations represent precise quantities. • But how do to relate the numbers of atoms or molecules to the amounts we measure out in the laboratory? • So, we must examine the masses of atoms and molecules. Stoichiometry © 2009, Prentice-Hall, Inc. ATOMIC MASS UNIT (amu) • The masses of individual atoms are extremely very small. • One atom of hydrogen (1H) has a mass of 1.6735 x 10-24 g • One atom of oxygen (16O) has a mass of 2.6560 x 10-23 g • It is convenient to use a unit called the atomic mass unit (amu): • 1 amu = 1.66054 x 10-24 g • The amu is defined by assigning a mass of exactly 12 amu to the 12C. Stoichiometry © 2009, Prentice-Hall, Inc. ATOMIC MASS UNIT (amu) • In these units the atomic weight : • Hydrogen (1H) atom is 1.0078 amu, • Oxygen (16O) = 15.9949 amu • Iron (56Fe) = 55.845 amu Stoichiometry © 2009, Prentice-Hall, Inc. AVERAGE ATOMIC MASS (ATOMIC WEIGHT) • Most elements occur in nature as mixture of isotopes • Atoms of a given element that differ in the number of neutrons, and consequently in mass, are called isotopes. • An atom of a specific isotope is called a nuclide. • We can determine the average atomic mass of an element by using the masses of its various isotopes and their relative abundances. • For example, naturally occuring carbon is composed of 98.892 percent of 12C and 1.108 % of 13C. • The masses of these nuclides are 12 amu and 13.00355 amu, respectively. • The average atomic mass (atomic weight) of carbon is: Stoichiometry 0.98892 *12 + 0.01108 * 13.00335 = 12.011 amu © 2009, Prentice-Hall, Inc. Formula Weights Stoichiometry © 2009, Prentice-Hall, Inc. Formula Weight (FW) • A formula weight is the sum of the atomic weights for the atoms in a chemical formula. • So, the formula weight (FW) of calcium chloride, CaCl2, would be Ca: 1(40.1 amu) + Cl: 2(35.5 amu) 111.1 amu • Formula weights are generally reported for ionic compounds. Stoichiometry © 2009, Prentice-Hall, Inc. Molecular Weight (MW) • If the chemical formula of a substance is its molecular formula, then the formula weight is also called the molecular weight. • A molecular weight is the sum of the atomic weights of the atoms in a molecule. • For the molecule ethane, C2H6, the molecular weight (MW) would be C: 2(12.0 amu) + H: 6(1.0 amu) 30.0 amu Stoichiometry © 2009, Prentice-Hall, Inc. Percent Composition from Formulas One can find the percentage of the mass of a compound that comes from each of the elements in the compound by using this equation: (number of atoms of that element)(atomic weight of element) x 100 % element = (FW of the compound) Stoichiometry © 2009, Prentice-Hall, Inc. Percent Composition So the percentage of carbon in ethane (C2H6) is… (2)(12.0 amu) %C = (30.0 amu) 24.0 amu x 100 = 30.0 amu = 80.0% Stoichiometry © 2009, Prentice-Hall, Inc. Avogadro’s Number and the Mole Stoichiometry © 2009, Prentice-Hall, Inc. The Mole Even the smallest samples that we deal with in the laboratory contain enormous numbers of atoms, ions, or molecules. For example, a teaspoon of water (about 5 mL) contains 2 X 10 23 water molecules? It is convenient to have a special unit for describing such large numbers of objects, like dozen (12 objects) and gross (144 objects). Stoichiometry © 2009, Prentice-Hall, Inc. The Mole is a convenient measure of chemical quantities. - A mole is defined as the amount of matter that contains as many objects (atoms, ions, or molecules) as the number of atoms in exactly 12 g of 12C. - The number of atoms in 12 g of 12C is 6.0221421 x 1023. - This number(6.0221421 x 1023) is called Avogadro’s number. - Thus, a mole of ions, a mole of molecules, or a mole of anything else all contain Avogadro’s number of these objects: 1 mole of carbon atoms = 6.02 x 1023 carbon atoms. 1 mol H2O molecules = 6.02 x 1023 H2O molecules. 1 mol NO3- ions = 6.02 x 1023 NO3- ions . Stoichiometry © 2009, Prentice-Hall, Inc. Molar Mass • By definition, a molar mass is the mass of 1 mol of a substance (i.e., g/mol). – The mass of a single atom of an element ( in amu) is numerically equal to the mass (in grams) of 1 mol of atoms of that element. One 12C atom weighs 12 amu 1 mol 12C weighs 12 g. One 24Mg atom weighs 24 amu 1 mol 24Mg weighs 24 g. One 197Au atom weighs 197 amu 1 mol 197Au weighs 197 g. Stoichiometry © 2009, Prentice-Hall, Inc. Molar Mass • The molar mass (in g/mol) of any substance is always numerically equal to its formula weight (in amu). One H2O molecule weighs 18.0 amu One NO3- ion weighs 62.0 amu One NaCl unit weighs 58.5 amu 1 mol H2O weighs 18 g. 1 mol NO3- weighs 62.0 g. 1 mol NaCl weighs 58.5 g. Stoichiometry © 2009, Prentice-Hall, Inc. Mole Relationships • One mole of atoms, ions, or molecules contains Avogadro’s number of those particles. • One mole of molecules or formula units contains Avogadro’s number times the number of atoms or ions of each element in the compound. Stoichiometry © 2009, Prentice-Hall, Inc. Empirical Formulas from analyses Stoichiometry © 2009, Prentice-Hall, Inc. Calculating Empirical Formulas The empirical formula for a substance tells us the relative number of atoms of each element it contains. Thus, the formula H2O indicates that the water contains two H atoms for each O atom. This ratio also applies on the molar level; Thus 1 mol of H2O contains 2 mol of H atoms and 1 mol of O atoms. Conversely, the ratio of the number of moles of each element in a compound gives the substcripts in a compounds empirical formula. Thus the mole concept provides a way of calculating the empirical formulas of Stoichiometry chemical substances. © 2009, Prentice-Hall, Inc. Example of calculating empirical formula The compound para-aminobenzoic acid (you may have seen it listed as PABA on your bottle of sunscreen) is composed of carbon (61.31%), hydrogen (5.14%), nitrogen (10.21%), and oxygen (23.33%). Find the empirical formula of PABA. Stoichiometry © 2009, Prentice-Hall, Inc. Calculating Empirical Formulas Assuming 100.00 g of para-aminobenzoic acid, C: H: N: O: 1 mol 12.01 g 1 mol 5.14 g x 1.01 g 1 mol 10.21 g x 14.01 g 1 mol 23.33 g x 16.00 g 61.31 g x = 5.105 mol C = 5.09 mol H = 0.7288 mol N = 1.456 mol O Stoichiometry © 2009, Prentice-Hall, Inc. Calculating Empirical Formulas Calculate the mole ratio by dividing by the smallest number of moles: C: 5.105 mol 0.7288 mol = 7.005 7 H: 5.09 mol 0.7288 mol = 6.984 7 N: 0.7288 mol 0.7288 mol = 1.000 O: 1.458 mol 0.7288 mol = 2.001 2 Stoichiometry © 2009, Prentice-Hall, Inc. Calculating Empirical Formulas These are the subscripts for the empirical formula: C7H7NO2 Stoichiometry © 2009, Prentice-Hall, Inc. Procedure used to Calculate Empirical Formulas Stoichiometry © 2009, Prentice-Hall, Inc. Calculating Molecular Formula from Empirical Formula We can obtain the molecular formula from the empirical formula if we known the molecular weight of the compound. The subscripts in the molecular formula of a compound are whole-number multiple of the subscripts in its empirical formula. Procedure of calcul Example: Mesitylene, a hydrocarbon that occurs in small amounts in crude oil, has an empirical formula of C3H4. The experimentally determined molecular weight of this substance is 121 amu. What is the molecular formula of mesitylene? Stoichiometry Solution: © 2009, Prentice-Hall, Inc. Plan The subscripts in the molecular formula of a compound are whole-number multiple of the subscripts in its empirical formula. To find the appropriate multiple, we must compare the molecular weight with the formula weight of the empirical formula. Solve First, we calculate the formula weight of the empirical formula, C3H4: 3(12.0 amu) + 4(1.0 amu) = 40.0 amu Next, we divide the molecular weight by the empirical formula weight to obtain the multiple used to multiply the subscripts in C 3H 4: Only whole-number ratios make physical sense because we must be dealing with whole atoms. The 3.02 in this case could result from a small experimental error in the molecular weight. We therefore multiply each subscript in the empirical formula by 3 to give the molecular formula: C9H12. Stoichiometry © 2009, Prentice-Hall, Inc. Practice Exercise Ethylene glycol, the substance used in automobile antifreeze, is composed of 38.7% C, 9.7% H, and 51.6% O by mass. Its molar mass is 62.1 g/mol. (a) What is the empirical formula of ethylene glycol? (b) What is its molecular formula? Answers: (a) CH3O, (b) C2H6O2 Stoichiometry © 2009, Prentice-Hall, Inc. Combustion Analysis • Compounds containing C, H and O are routinely analyzed through combustion in an apparatus like this. • CuO (copper oxide) helps to oxide traces of carbon and carbon monoxide to carbon dioxide and to oxide hydrogen to water Stoichiometry © 2009, Prentice-Hall, Inc. Calculating Empirical Formula from Combustion Analysis When a compound containing carbon and hydrogen is completely combusted in this apparatus, all the carbon and hydrogen are converted to CO2 and H2O, respectively. From the masses of CO2 and H2O we can calculate the number of moles of C and H in the compound and thereby the empirical formula. If the compound contains a third element, its mass can be determined by subtracting the masses of C and H from the compound's original mass. Stoichiometry © 2009, Prentice-Hall, Inc. Calculating Empirical Formula from Combustion Analysis Example: Isopropyl alcohol, a substance sold as rubbing alcohol, is composed of C, H, and O. Combustion of 0.255 g of isopropyl alcohol produces 0.561 g of CO2 and 0.306 g of H2O. Determine the empirical formula of isopropyl alcohol. Solution Solve To calculate the number of grams of C, we first use the molar mass of CO 2, 1 mol CO2 = 44.0 g CO2, to convert grams of CO2 to moles of CO2. Because each CO2 molecule has only 1 C atom, there is 1 mol of C atoms per mole of CO2 molecules. This fact allows us to convert the moles of CO2 to moles of C. Finally, we use the molar mass of C, 1 mol C =1 2.0 g C, to convert moles of C to grams of C. Combining the three conversion factors, we have The calculation of the number of grams of H from the grams of H2O is similar, although we must remember that there are 2 mol of H atoms per 1 mol of H2O molecules: The total mass of the sample, 0.255 g, is the sum of the masses of the C, H, and O. Thus, we can calculate the mass of O as follows: Stoichiometry © 2009, Prentice-Hall, Inc. Calculating Empirical Formula from Combustion Analysis We then calculate the number of moles of C, H, and O in the sample: To find the empirical formula, we must compare the relative number of moles of each element in the sample. The relative number of moles of each element is found by dividing each number by the smallest number, 0.0043. The mole ratio of C:H:O so obtained is 2.98:7.91:1.00. The first two numbers are very close to the whole numbers 3 and 8, giving the empirical formula C3H8O. Stoichiometry © 2009, Prentice-Hall, Inc. Calculating Empirical Formula from Combustion Analysis Practice Exercise a) Caproic acid, which is responsible for the foul odor of dirty socks, is composed of C, H, and O atoms. Combustion of a 0.225-g sample of this compound produces 0.512 g CO2 and 0.209 g H2O. What is the empirical formula of caproic acid? (b) Caproic acid has a molar mass of 116 g/mol. What is its molecular formula? Answers: (a) C3H6O, (b) C6H12O2 Stoichiometry © 2009, Prentice-Hall, Inc. Quantitative information from balanced equations aA + bB cC + dD If a reaction occurs stoichiometrically, the relationship between the quantities of the substances are: nA/a = nB/b = nC/c = nD/d nA, nB, nC, nD, quantities (mol) of formed products and reacted reactants Stoichiometry © 2009, Prentice-Hall, Inc. Limiting Reactants Stoichiometry © 2009, Prentice-Hall, Inc. Limiting Reactants The number of moles of O2 needed to react with all the 10 moles of H2 is : nH2/2 = 10/2 = nO2/1 nO2= 5 Because 7 mol O2 was available at the start of the reaction, 7 -5 = 2 mol O2 will be present when the H2 is all consumed. • The reactant that is completely consumed in the reaction is called the limiting reactant because it determines, or limits, the amount of product formed. The other reactant is called excess reactant. Stoichiometry • In our example, H2 is the limiting reactant, and O2 is the excess © 2009, Prentice-Hall, Inc. reactant or excess reagent. Limiting Reactants • The limiting reactant is the reactant present in the smallest stoichiometric amount. • In other words, it’s the reactant you’ll run out of first – The quantity of limiting reactant is used to calculate the quantity of any product formed In our case, the number of moles of H2O formed is : nH2/2 = 10/2 = nH2O/2 nH2O= 10 Stoichiometry © 2009, Prentice-Hall, Inc. Theoretical and Actual Yields • The quantity of product that is calculated to form when all of the limiting reactant reacts is called the theoretical yield. • The amount of product actually obtained in the reaction is called the actual yield. • The actual yield is always less than the theoretical yield. Stoichiometry © 2009, Prentice-Hall, Inc. Percent Yield One finds the percent yield by comparing the amount actually obtained (actual yield) to the amount it was possible to make (theoretical yield). Actual Yield Percent Yield = Theoretical Yield x 100 Stoichiometry © 2009, Prentice-Hall, Inc. Percent Yield Consider the following reaction: 2 NaPO4(aq) + 3 Ba(NO3)2 (aq) Ba3(PO4)2 (s) + 6 NaNO3 (aq) 4.92 g of Ba3(PO4)2 should form when 3.50 g of NaPO4 is mixed with 6.40 g of Ba(NO3)2 . If the actual yield turned out to be 4.70 g, calculate the percent yield? The theoretical yield is 4.92 g, then the percent yield is: (4.70g/4.92 g ) x 100 % = 95.5 % Stoichiometry © 2009, Prentice-Hall, Inc. Solution Stoichiometry © 2009, Prentice-Hall, * A solution is a homogeneous mixture of two or more substances * One of these substances is called the solvent; it is present in greater quantity * The other substances in the solution are the solutes Stoichiometry © 2009, Prentice-Hall, Inc. Ways of Expressing Concentrations of Solutions Stoichiometry © 2009, Prentice-Hall, Molarity • Two solutions can contain the same compounds but be quite different because the proportions of those compounds are different. • Molarity is one way to measure the concentration of a solution. Molarity (M) = moles of solute volume of solution in liters M = n(mol)/V (L) n (mol) = M x V (L) •Since volume is temperature-dependent, molarity Stoichiometry can change with temperature. © 2009, Prentice-Hall, Inc. Molality (m) m= mol of solute kg of solvent Since both moles and mass do not change with temperature, molality (unlike molarity) is not temperaturedependent. Stoichiometry © 2009, Prentice-Hall, Mole Fraction (X) moles of A XA = total moles in solution • In some applications, one needs the mole fraction of solvent, not solute — make sure you find the quantity you need! Stoichiometry © 2009, Prentice-Hall, Mass Percentage mass of A in solution 100 Mass % of A = total mass of solution Stoichiometry © 2009, Prentice-Hall, Parts per Million and Parts per Billion Parts per Million (ppm) mass of A in solution 106 ppm = total mass of solution Parts per Billion (ppb) mass of A in solution 109 ppb = total mass of solution -The mass units of the solute and solution should be the same. Stoichiometry © 2009, Prentice-Hall, Changing Molarity to Molality If we know the density of the solution, we can calculate the molality from the molarity and vice versa. Stoichiometry © 2009, Prentice-Hall, Mixing a Solution • To create a solution of a known molarity, one weighs out a known mass (and, therefore, number of moles) of the solute. • The solute is added to a volumetric flask, and solvent is added to the line on the neck of the flask. Stoichiometry © 2009, Prentice-Hall, Inc. Dilution • One can also dilute a more concentrated solution by – Using a pipet to deliver a volume of the solution to a new volumetric flask, and – Adding solvent to the line on the neck of the new flask. Stoichiometry © 2009, Prentice-Hall, Inc. Dilution The molarity of the new solution can be determined from the equation Mc Vc = Md Vd, where Mc and Md are the molarity of the concentrated and dilute solutions, respectively, and Vc and Vd are the volumes of the two solutions. Stoichiometry Vc Vd © 2009, Prentice-Hall, Inc. Practice exercise • What is the volume (in ml) required to dilute 220 ml of 1.75 M HCl to exactly 1.25 M Stoichiometry © 2009, Prentice-Hall, Inc. Solution • • • • • Mc x Vc = Md x Vd 1.75 x 220 = 1.25 x Vd Vd = (1.75 x 220)/1.25 = 308 mL The volume required of water is V = 308 – 220 = 88 mL Stoichiometry © 2009, Prentice-Hall, Inc. Using Molarities in Stoichiometric Calculations Stoichiometry © 2009, Prentice-Hall, Inc. One finds the percent yield by comparing the amount actually obtained (actual yield) to the amount it was possible to make (theoretical yield). Actual Yield Percent Yield = Theoretical Yield x 100 Stoichiometry © 2009, Prentice-Hall, Inc.