CHAPTER 2

Atoms, Molecules & Stoichiometry

Learning Outcomes
define the terms relative atomic, isotopic, molecular and formula

masses, based on the 12C scale define the term mole in terms of the Avogadro constant analyse mass spectra in terms of isotopic abundances calculate the relative atomic mass of an element given the relative abundances of its isotopes, or its mass spectrum define the terms empirical and molecular formulae calculate empirical and molecular formulae, using combustion data or composition by mass write and/or construct balanced equations

Learning Outcomes
perform calculations, including use of the mole concept, involving:

(i) reacting masses (from formulae and equations) (ii) volumes of gases (e.g. in the burning of hydrocarbons) (iii) volumes and concentrations of solutions deduce stoichiometric relationships from calculations describe and explain redox processes in terms of electron transfer and/or of changes in oxidation number (oxidation state) (calculation of oxidation number is required)

Relative Mass
Relative Formula Mass
- Ratio of the average mass of one formula unit of the compound to 1/12 the mass of an atom of 12C isotope, expressed on the 12C scale

Relative Atomic Mass

- Ratio of the average mass of one atom of the element to 1/12 the mass of an atom of 12C isotope, expressed on the 12C scale

Relative Mass
Relative Isotopic Mass
- Ratio of the mass of one atom of the isotope to 1/12 the mass of an atom of 12C isotope, expressed on the 12C scale

Relative Molecular Mass

- Ratio of the average mass of one molecule of the substance to 1/12 the mass of an atom of 12C isotope, expressed on the 12C scale

A Mole of Atoms
A mole is a collection that contains
6.02 x 1023 atoms of an element (Avogadros

number). 1 mole element 1 mole C 1 mole Na 1 mole Au Number of Atoms = 6.02 x 1023 C atoms = 6.02 x 1023 Na atoms = 6.02 x 1023 Au atoms

A Mole of a Compound
A mole
Of a covalent compound has Avogadros number of

molecules. 1 mole CO2 = 6.02 x 1023 CO2 molecules

1 mole H2O = 6.02 x 1023 H2O molecules

Of an ionic compound contains Avogadros number

of formula units. 1 mole NaCl = 6.02 x 1023 NaCl formula units 1 mole K2SO4 = 6.02 x 1023 K2SO4 formula units

One Mole of Four Elements

One mole each of helium, sulfur, copper, and mercury.

How many atoms of helium are present? Of sulfur? Of copper? Of mercury?

Using Avogadros Number

Avogadros number is used to convert moles of a substance to particles. How many Cu atoms are in 0.50 mole Cu? 0.50 mole Cu x 6.02 x 1023 Cu atoms 1 mole Cu = 3.0 x 1023 Cu atoms

Using Avogadros Number

Avogadros number is used to convert particles of a substance to moles. How many moles of CO2 are in 2.50 x 1024 molecules CO2? 2.50 x 1024 molecules CO2 x 1 mole CO2

6.02 x 1023 molecules CO2

= 4.15 moles CO2

Molar Mass
The molar mass is The mass of one mole of a substance. The atomic mass of an element expressed in grams.

AVERAGE ATOMIC MASS

The mass spectrometer is an instrument used to measure the masses and relative (natural) abundances of the isotopes present in a sample of an element

Mass Spectrometer
In a mass spectrometer, charged particles are passed through a magnetic field. The path of the stream of particles will be bent by the magnetic field depending on the mass and charge of the particles. When naturally occurring samples of most elements are charged and passed through a mass spectrometer, the spectrum indicates more than one form of the element. These are isotopes of the element: the number of protons is the same but the number of neutrons/atom differs for each isotope giving each isotope a slightly different mass.

Mass Spectrometer

There are 2 isotopes for boron: boron-10 23

boron-11

100

Suppose you had 123 typical atoms of boron. 23 of these would be 10B and 100 would be 11B.
The total mass of these would be (23 x 10) + (100 x 11) = 1330 The average mass of these 123 atoms would be 1330 / 123 = 10.8 (to 3 significant figures). 10.8 is the relative atomic mass of boron.

The data can be summarized as follows: Isotope Mass` 90Zr 90.00 amu 91Zr 91.00 amu 92Zr 92.00 amu 94Zr 94.00 amu 96Zr 96.00 amu atomic mass of isotope

Abundance 51.5 % 11.2 % 17.1 % 17.4 % 2.80 % 100 %

Calculate the weighted average mass of zirconium using the data below. Change each percent to a decimal by dividing by 100. Multiply by the mass. Add it all together.
Isotope 90Zr 91Zr 92Zr 94Zr 96Zr Mass` 90.00 amu 91.00 amu 92.00 amu 94.00 amu 96.00 amu Abundance 51.5 % 11.2 % 17.1 % 17.4 % 2.80 %

0.515(90.00) + 0.112(91.00) + 0.171(92.00) + 0.174(94.00) + 0.0280(96.00)

= 91.3 amu

Calculate the average atomic mass for Germanium

36.54 % 73.92115 amu

27.43 % 71.92174 amu 20.52 % 69.92428 amu 7.76 % 72.9234 amu 7.76 % 75.9214 amu

The mass spectrum of chlorine

Chlorine consists of molecules, not individual atoms. When chlorine is passed into the ionisation chamber, an electron is knocked off the molecule to give a molecular ion, Cl2+. These ions won't be particularly stable, and some will fall apart to give a chlorine atom and a Cl+ ion.

Empirical and Molecular Formula

The empirical formula of a compound is the simplest formula which shows the ratio of the atoms of the different elements in the compound.

Question: 69.58% Ba, 6.090% C, 24.32% O. What is the empirical formula? Assume you have 100 g of sample, 1: 69.58 g Ba, 6.090 g C, 24.32 g O 2: Ba: C: O: 69.58 g 6.090 g 24.32 g 137.33 g/mol 12.01 g/mol 16.00 g/mol = = = 0.50666 mol Ba 0.50708 mol C 1.520 mol O

Empirical Formula
3. mol mol (reduced) Ba 0.50666 C 0.50708 O 1.520

0.50666/ 0.50666
=1

0.50708/ 0.50666
= 1.001

1.520/ 0.50666
= 3.000

4: the simplest formula is BaCO3

Empirical Formula

y CxHy + (x+ )O2(g) 2

y x CO2(g) + H2O(g) 2

EXAMPLE 3.19 PROCEDURE FOR... Obtaining an Empirical Formula from Combustion Analysis
1. Write down as given the masses of

Obtaining an Empirical Formula from Combustion Analysis Upon combustion, a compound containing only carbon and hydrogen produces 1.83 g CO2 and 0.901 g H2O. Find the empirical formula of the compound. GIVEN: 1.83 g CO2, 0.901 g H2O FIND: empirical formula

each combustion product and the mass of the sample (if given). 2. Convert the masses of CO2 and H2O from step 1 to moles by using the appropriate molar mass for each compound as a conversion factor.

3. Convert the moles of CO2 and

moles of H2O from step 2 to moles of C and moles of H using the conversion factors inherent in the chemical formulas of CO2 and H2O.
continued
2011 Pearson Education, Inc.

4. If the compound contains an element other than C and H, find the mass of the other element by subtracting the sum of the masses of C and H (obtained in step 3) from the mass of the sample. Finally, convert the mass of the other element to moles.
5. Write down a pseudoformula for the

No other elements besides C and H, so proceed to next step.

C0.0416H0.100

compound using the number of moles of each element (from steps 3 and 4) as subscripts.
6. Divide all the subscripts in the formula

by the smallest subscript. (Round all subscripts that are within 0.1 of a whole number.) 7. If the subscripts are not whole numbers, multiply all the subscripts by a small whole number to get whole-number subscripts.

The correct empirical formula is C5H12.

2011 Pearson Education, Inc.

Molecular Formula
The molecular formula of a compound is one which shows the actual number of atoms of each element present in one molecule of a compound. The molecular formula can be obtained if the empirical formula and Mr are known. Example: A compound has the empirical formula CH2Br. Its relative molecular mass is 187.8. Deduce the molecular formula of this compound. n(CH2Br) = 187.8 n(93.9) = 187.8 n=2 Molecular formula = C2H4Br2

Chemical Formula and Mole Concept

The subscripts in a formula give The relationship of atoms in the formula. The moles of each element in 1 mole of compound. Glucose C6H12O6
In 1 molecule: 6 atoms C 12 atoms H In 1 mole: 6 moles C 12 moles H 6 atoms O 6 moles O

Writing and Balancing Chemical Equation

Chemical equation Uses chemical symbols and chemical formulas to

describe the changes occur in a chemical reaction

Reactant is a starting material Written on left side Product is a substance produced Written on right side CH4 + 2O2
Reactant

CO2 + 2H2O
Product

Law of Conservation of Mass

The Law of Conservation of Mass indicates that in an ordinary chemical reaction, Matter cannot be created or destroyed. No change in total mass occurs in a reaction. Mass of products is equal to mass of reactants.

Writing and Balancing Chemical Equation

Example: 2Ag + S Ag2S in this equation the number of reactants are equal to that of the products.(2 Ag and 1 S)

Balance the following chemical equations. Fe(s) + S(s) NH3 + O2 HCl + O2 Fe2S3(s) N2 + H2O Cl2 + H2O

Chemical Equations and The Mole Concept

a chemical equation indicates the relative amounts of each reactant and product in a given chemical reaction. Example: CH4 + 2O2 CO2 + 2H2O The equation shows that 1 mol of methane reacts with 2 mol of oxygen to produce 2 mol of water.

Chemical Calculations Using Chemical Equations

A balanced chemical equation can be used to calculate the

relative amounts of substances involved in chemical reactions.

Example:
When 18.6 g ethane gas C2H6 burns in oxygen, how many grams of CO2 are produced? 2C2H6(g) + 7O2(g) 18.6 g 4CO2(g) + 6H2O(g) ?g

Chemical Calculations Using Chemical Equations

Solution:
g C2H6 mole C2H6
molar mass C2H6

mole CO2 g CO2 mole-mole molar factor mass CO2

= 18.6 g C2H6 x 1 mole C2H6 x 4 moles CO2 x 44.0 g CO2 30.1 g C2H6 2 moles C2H6 1 mole CO2 molar mole-mole molar mass C2H6 factor mass CO2 = 54.4 g CO2

Balancing Ionic Equations

When ionic compounds dissolve in water, the ions separate from each

other. Example : NaSO4 (s) + aq Na+ (aq) + SO4-2 (aq)

The ions that play no part in the reaction are called spectator ions.

Molecular Equation: K2CrO4 + Pb(NO3)2

Soluble Soluble

PbCrO4 + 2 KNO3
Insoluble Soluble

Total Ionic Equation:(cancelling spectator ions) 2 K+ + CrO4 -2 + Pb+2 + 2 NO3- PbCrO4 (s) + 2 K+ + 2 NO3Net Ionic Equation: CrO4 -2 + Pb+2 PbCrO4 (s)

Limiting Reactants
Cookies Analogy:
You can make cookies

until you run out of one of the ingredients Sugar is the limiting ingredient in making the cookies (present in small amount). Sugar will limit the amount of cookies you can make

Limiting Reactants
The limiting reactant is the reactant present in

the smallest stoichiometric amount

In other words, its the reactant youll run out of first (in this case, the H2) O2 would be the excess reagent

Theoretical yield Maximum amount of product that can be obtained in a reaction from the given amounts of reactant. Percentage yield A comparison of the amount actually obtained to the amount it was possible to make.
Percent Yield= Actual Yield Theoretical Yield x 100

 Silicon dioxide (quartz) is usually quite unreactive but reacts

readily with hydrogen fluoride according to the following equation.

LR

SiO2(s) + 4HF(g)
4.5 mol 2.0 mol

SiF4(g) + 2H2O(l)
? mol

If 2.0 mol of HF are exposed to 4.5 mol of SiO2, which is the limiting reactant?

LR 1 mol SiO2 2.0 mol HF x 4 mol HF

0.5 mol SiO2

(smaller number)

4.5 mol SiO2 x

4 mol HF 1 mol SiO2

18 mol HF

Calculations Involving Volumes of Gases

One mole of any gas occupies a volume of 22.4 dm3 at

s.t.p. (or 24 dm3 at r.t.p) This is the molar volume of gases.

Example:

1. What volume is occupied by 4.21 moles of ammonia gas, NH3 at STP?

4.21 mol 22.4 L 1 mole = 94.3 L

Calculations Involving Volumes of Gases

2. What volume of hydrogen, measured at STP, can be released by 42.7 g of zinc as it reacts with hydrochloric acid?
Zn (s) + 2 HCl (aq) H2 (g) + ZnCl2 (aq)

42.7 g Zn

1 mol Zn 65.4 g Zn

1 mol H2 1 mol Zn

22.4 L H2 1 mol H2

= 14.6 L H2

39

Solutions and Solution Stoichiometry

Solute: the substance being dissolved. Solvent: the substance doing the dissolving. Concentration of a solution: the quantity of a solute in a given quantity of solution (or solvent).
A concentrated solution contains a relatively large amount of solute vs. the solvent (or solution). A dilute solution contains a relatively small concentration of solute vs. the solvent (or solution). Concentrated and dilute arent very quantitative

Prentice Hall 2005

General Chemistry 4th edition, Hill, Petrucci, McCreary, Perry

Chapter Three

CONCENTRATION OF AQUEOUS SOLUTION

The concentration of aqueous solution may be expressed either as: a) mass of solute per dm3 of solution (units: g dm-3 ) or b) mol of solute per dm3 of solution (units: mol dm-3 )

41

Molar Concentration
Molarity (M), or molar concentration, is the amount of solute, in moles, per liter of solution: moles of solute Molarity = liters of solution A solution that is 0.35 M sucrose contains 0.35 moles of sucrose in each liter of solution. Keep in mind that molarity signifies moles of solute per liter of solution, not liters of solvent.
Prentice Hall 2005
General Chemistry 4th edition, Hill, Petrucci, McCreary, Perry

Chapter Three

42

Preparing 0.01000 M KMnO4

Weigh 0.01000 mol (1.580 g) KMnO4.

Prentice Hall 2005

Dissolve in water. How much water? Doesnt matter, as long as we dont go over a liter.
General Chemistry 4th edition, Hill, Petrucci, McCreary, Perry

Add more water to reach the 1.000 liter mark.

Chapter Three

43

Dilution of Solutions
Dilution is the process of preparing a more dilute solution by adding solvent to a more concentrated one. Addition of solvent does not change the amount of solute in a solution but does change the solution concentration. It is very common to prepare a concentrated stock solution of a solute, then dilute it to other concentrations as needed.
Prentice Hall 2005
General Chemistry 4th edition, Hill, Petrucci, McCreary, Perry

Chapter Three

Visualizing the Dilution of a Solution

44

We start and end with the same amount of solute.

Addition of solvent has decreased the concentration.

Prentice Hall 2005

General Chemistry 4th edition, Hill, Petrucci, McCreary, Perry

Chapter Three

45

Dilution Calculations
couldnt be easier. Moles of solute does not change on dilution. Moles of solute = M V Therefore
Mconc Vconc = Mdil Vdil

Prentice Hall 2005

General Chemistry 4th edition, Hill, Petrucci, McCreary, Perry

Chapter Three

Example 3.26
How many milliliters of a 2.00 M CuSO4 stock solution are needed to prepare 0.250 L of 0.400 M CuSO4?

46

Prentice Hall 2005

General Chemistry 4th edition, Hill, Petrucci, McCreary, Perry

Chapter Three

Acid-Base Titrations
Acid-base titration

A neutralization reaction in which a measured volume of an

acid or a base of known concentration is completely reacted with a measured volume of a base or an acid of unknown

concentration
Acid-base indicator

A compound that exhibits different colours depending on the

pH of its solution

Setup for titrating an acid with a base

Acid-Base Titrations
The unknown concentration of the base or acid can be

calculated by using this formula:

M1V1 = M2V2

SAMPLE PROBLEM
In an acid-base titration, 17.45 mL of 0.180 M

nitric acid, HNO3, were completely neutralized by 14.76 mL of aluminium hydroxide, Al(OH)3. Calculate the concentration of the aluminium hydroxide.

SAMPLE ANSWER
The balanced equation for the reaction is:

3HNO3(aq) + Al(OH)3(aq) Al(NO3)3(aq) + 3H2O(l)

The number of moles of nitric acid used is:

y mol = 0.180 mol/L x 0.01745 L = 3.14 x 10-3 mol HNO3

From the stoichiometry of the reaction, the number of moles of

aluminium hydroxide reacted is: 3.14 x 10-3 mol HNO3 x 1 mol Al(OH)3 = 1.05 x 10-3 mol 3 mol HNO3
Therefore, the concentration of the aluminium hydroxide is:

1.05 x 10-3 mol Al(OH)3 = 0.0711 M 0.01476 L

EXERCISE

If 30 mL of 0.5 M HCl neutralizes 20.40 mL of Ba(OH)2 solution, what is the molarity of the Ba(OH)2 solution? You have to write a balanced equation for the neutralization.

Redox Reactions
Oxidation-reduction (redox) reaction:
A chemical reaction in which there is a transfer of

electrons from one reactant to another reactant. Oxidation number of an atom is the charge that atom would have if the compound was composed of ions.

Redox Reactions
Rules for determining oxidation numbers: Zero for element in its elemental state Equal to the charge for the monatomic ion For Groups IA and IIA in compounds always +1, +2 +1 for hydrogen in most compounds -2 for oxygen in most compounds In binary compounds, the more electronegative element is assigned a negative oxidation number (as in its binary ionic compounds) The sum of the individual oxidation numbers is equal to zero for a neutral compound, equal to the charge on the polyatomic ion

Oxidation number
The charge the atom would have in a molecule (or an ionic compound) if electrons were completely transferred.

1. Free elements (uncombined state) have an oxidation number of zero.

Na, Be, K, Pb, H2, O2, P4 = 0

2. In monatomic ions, the oxidation number is equal to the charge on the ion.

Li+, Li = +1; Fe3+, Fe = +3; O2-, O = -2

3. The oxidation number of oxygen is usually 2. In H2O2 and O22- it is 1.

4. The oxidation number of hydrogen is +1 except when it is bonded to metals in binary compounds. In these cases, its oxidation number is 1. 5. Group IA metals are +1, IIA metals are +2 and fluorine is always 1. 6. The sum of the oxidation numbers of all the atoms in a molecule or ion is equal to the charge on the molecule or ion.

HCO3Oxidation numbers of all the elements in HCO3- ?

O = -2

H = +1

3x(-2) + 1 + ? = -1
C = +4

Oxidation numbers of all the elements in the following ?

NaIO3 Na = +1 O = -2

K2Cr2O7 O = -2 K = +1

3x(-2) + 1 + ? = 0
I = +5

7x(-2) + 2x(+1) + 2x(?) = 0 Cr = +6