Atoms, Moles and Stoichiometry

Atoms, Moles and Stoichiometry

Relative Masses of Atoms and Molecules

Candidates should be able to define the terms relative atomic, isotopic, molecule
formula masses, based on the 12C scale.

The 12C scale is one on which an atom of 12C isotope is assigned a mass of exactly
12.000 units.

Relative Atomic The relative atomic mass, Ar, of an element is defined as the ratio of the average
1
Mass mass of one atom of the element to the mass of an atom of l2C isotope, expressed
12
on the l2C scale.

mass of one atom of an element

Ar =
1
mass of an atom of 12C isotope
12

Relative Isotopic The relative iostopic mass, Ar, of a particular isotope is defined as the ratio of the
1
Mass mass of one atom of the isotope to the mass of an atom of 12C isotope, expressed
12
on the 12C scale.

mass of one atom of a certain isotope

Ar =
1
mass of an atom of 12C isotope
12

Relative The relative molecular mass, Mr, of a substance is defined as the ratio of the
1
Molecular Mass average mass of one molecule of the substance to the mass of an atom of 12C
12
isotope, expressed on the 12C scale.

mass of one molecule of the substance

Mr =
1
mass of an atom of 12C isotope
12

Mr can be simply taken to be the sum of the Ar of all the atoms shown in the formula
of the substance; e.g. Mr of CaCO3 = 40.1 + 12.0 + 3(16.0) = 100.1

Relative The relative formula mass of an ionic compound, Mr, is defined as the ratio of the
1
Formula Mass average mass of one formula unit of the compound to the mass of an atom of 12C
12
isotope, expressed on the 12C scale.

mass of one formula unit of the compound

Mr =
1
mass of an atom of 12C isotope
12

The term relative formula mass is used for all ionic and giant molecular
compounds, which do not form simple molecular entities.
Mr can be simply taken to be the sum of the Ar of all the atoms shown in the
formula unit of the compound; the charge on the ion is ignored.
e.g. Mr of CO32+ = 12.0 + 3(16.0) = 60.0

[NB. All the relative masses, both Ar and Mr have no units since they are ratios.]

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 Atoms, Moles and Stoichiometry

The Mole, the Avogardo Constant

Candidates should be able to define the term mole in terms of the Avogadro constant

Mole The mole is the unit of the amount of substance.

One mole of a substance contains as many particles (or elementary entities) of that
substance as there are atoms of carbon in 12 grams (0.012 kg) of carbon12.
Identities of the particles must be stated (e.g. atoms, molecules, ions, electrons).

Avogardo The Avogadro constant, L, may be taken as the number of carbon atoms in 12 g of
Constant carbon12, and has been determined experimentally to have a value of about
6.02 x 1023 mol1 (3 sf). Equivalently,

One mole of any substance is the amount of substance containing a number of

particles equal to the Avogadro constant.

e.g. 1 mol of 12C atoms= 6.02 x 1023 12C atoms

1 mol of H2O molecules = 6.02 x1023 H2O molecules
1 mol of CO32 ions = 6.02 x 1023 CO32 ions
1 mol of electrons = 6.02 x 1023 electrons

A mole of any substance has a mass in grams numerically equal to its Ar or Mr.

e.g. mass of 1 mol of 12C atoms = 12 g

mass of 1 mol of H2O molecules = [2(1) + 16] g = 18 g
mass of 1 mol of CO32 ions = [12 + 3(16)] g = 60 g

Hence, a phrase such as '16 g of oxygen' is ambiguous.

It could mean 16 g of oxygen atoms (O), 16 g of oxygen molecules (O2) or 16 g

of oxygen ions (O2).
It could also mean 16 g of 16O isotope or 16 g of 18O isotope.

Relationship between the number of moles (n), mass (m) and relative masses:

m m where m = mass in grams

n or n Ar = relative atomic mass
Ar Mr
Mr = relative molecular mass

Relationship between the number of particles, moles (n), and Avogadro constant
(L):
no. of particles = nL where L = 6.02 x 1023 mol-1.

Question
(a) What is the mass of one mole of aspirin, C9H8O4?
(b) How many moles of asprin are there in 1.00 g of this substance?
(c) What is the mass, in grams, of 0.433 mol of aspirin?
(d) How many aspirin molecules are there in 1.74 g of this substance?
(e) What is the mass, in grams, of 1.00 x 1023 molecules of aspirin?
(f) How many carbon atoms are there in 1 mol of aspirin?

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 Atoms, Moles and Stoichiometry

Determination of Ar and Mr from Mass Spectra

Mass In a mass spectrometer, positive ions are produced by bombarding the vaporised
Spectrometer sample with high energy electrons. The ions are accelerated by an electric field into
the magnetic field, which causes the ions to be deflected from their straight-line
paths. The extent of deflection depends on the mass-to-charge ratio (m/e) of the
ion.

A lighter ion is deflected more than a heavier one with the same charge.
A doubly charged ion is deflected more than a singly charged ion of the same
mass.

Candidates should be able to

(a) analyse mass spectra in terms of isotopic abundances and molecular fragments.
(b) calculate the relative atomic mass of an element given the relative abundances of
its isotopes, or its mass spectrum.

A mass spectrum is a plot of relative abundance against m/e. It shows where the ion
appears and how many ions appear.

Mass Spectra of The mass spectrum of an element provides the following information:
Elements
1. number of isotopes present - from the number of peaks or lines.
2. isotopic mass and hence, identity of the isotope - from m/e value of each peak.
3. relative abundance of each isotope - from the height of each peak.

The relative atomic mass, Ar, of an element is the weighted average of the isotopic
masses according to their relative abundance.

Ar
isotopic mass percentage abundance
100

e.g. 1: Mass spectrum o f chlorine

Chlorine consists of two isotopes, 35Cl and 37Cl.

Relative abundance of 35Cl : 37Cl = 3:1
(or 75% : 25%).

75 35 25 37 35.5
Ar of Cl = 100

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e.g. 2: Mass spectrum o f lead

Lead consists of four isotopes (204Pb, 206Pb,

207Pb and 208Pb).

Relative abundance: 2%, 24%, 22% and 52%

respectively.

Ar of P b =
2 204 24 206 22 207 52 208 207.22
100

Mass Spectra of When a compound is analysed in a mass spectrometer, it undergoes fragmentation.

Compounds Positive ions are produced (as with atoms) and detected.

The mass spectrum of a compound provides the following information:

1. identity of fragment ions - from the m/e value of each peak or line.
2. identity of molecular ion and hence, the relative molecular mass of the
compound - from the highest m/e value.
3. relative abundance of fragment ions or molecular ion - from the height of peak.

If one of the elements in the molecule consists of two or more isotopes, then more
than one line is produced by the molecular ion.
(See Mass spectrum of 12C21H4Br2 in e.g. 4 )

e.g. 3: Mass spectrum of sulphur vapour

The most abundant species is S2 (at m/e

64, the tallest line).
The molecular ion is S8 (at m/e 256, the
highest m/e value) and Mr of sulphur
vapour is 256.

e.g. 4: Mass spectrum o f 12C21H4Br2

Bromine occurs naturally as two

isotopes, and , in equal
abundance. Hence, three lines are
produced by the molecular ion of
12C21H4Br2 at m/e 186, 188 and 190 (with

relative intensity 1:2:1).

m/e species relative

abundance

186 [C2H479Br2]+ =

188 [C2H479Br 81Br]+ 2=

190 [C2H481Br2]+ =

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 Atoms, Moles and Stoichiometry

Uses of Mass A mass spectrometer can be used to determine

Spectrometer the relative atomic mass, Ar, of an element.
the relative molecular mass, Mr, of a compound.
the accurate mass of an individual nuclide.
the identity of compounds from their characteristic spectra.

Q1. Naturally occurring gallium, Ga, is a mixture of two isotopes of mass numbers 69 and
71. What is the percentage abundance of each isotope? [Ar of Ga = 69.7]

Q2. Chlorine consists of two isotopes, 35Cl and 37CI, in the abundance ratio 3:1.
Phosphorus is mono-isotopic, 31P.

group m/e values of lines

A 66, 68
B 101, 103, 105
C 136, 138, 140, 142

Apart from lines due to atomic ions, the mass spectrum of a chloride of phosphorus
contains 9 lines arranged in 3 groups:

(a) Identify the ions responsible for each group of lines.

(b) Predict the abundance ratios of the various m/e values within each group.
(c) What apparent mass number would register on the mass spectrometer scale if
the heaviest of these ions acquired a second charge?

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 Atoms, Moles and Stoichiometry

Empirical and Molecular Formulae

Candidate should be able to

(a) define the terms empirical and molecular formulae.
(b) calculate empirical and molecular formulae, using combustion data or
composition by mass.

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

Molecular The molecular formula of a compound is one which shows the actual number of
Formula 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.

Calculation Steps to follow:

from 1. Change percentage composition to mass, m (in g).
Composition by 2. Divide the mass of each element by its respective atomic mass to get the number
of moles of each.
Mass
3. Divide the number of moles of each element by the smallest number of moles.
This usually gives whole number ratios of moles.
4. If a fraction still exists,
(a) Change the decimal portion to a fraction.
(b) Change compound fractions to simple fractions.
(c) Multiply all numbers obtained in step 3 by the denominator of the fraction,
e.g. ratio 3.5 : 1 = : 1 = 7 : 2

eg. Calculate the empirical formula of a compound that has the composition: 12.8 % carbon, 2.1 %
hydrogen and 85.1 % bromine.

eg. Calculate the empirical formula of a compound that has the composition: 48.8 % carbon, 13.5 %
hydrogen and 37.7 % nitrogen.

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 Atoms, Moles and Stoichiometry

Calculation The molecular formula of hydrocarbons can be determined by combustion in excess

using oxygen (to form carbon dioxide and steam). A gaseous hydrocarbon, C xHy,
Combustion explodes with excess O2 according to the general equation:
Data
CxHy + (x + )O2 x CO2 + H 2O

Examples
Q1. 10 cm3 of a gaseous hydrocarbon required 20 cm 3 of oxygen for complete
combustion. 10 cm3 of carbon dioxide was produced. Calculate the molecular
formula of the hydrocarbon. [All gases were measured under the same conditions.]

Q2. 150 cm3 of oxygen were added to 20 cm 3 of a gaseous hydrocarbon. After explosion
and cooling, the gaseous mixture occupied 130 cm 3 and, after absorption by
potassium hydroxide, 90 cm3 of oxygen remained. Calculate the molecular formula
of the hydrocarbon. [All volumes being measured at r.t.p.]

Q3. Complete combustion of a hydrocarbon yields 2.64 g of carbon dioxide and 0.540 g
of water. What is the empirical formula of the hydrocarbon? If the relative molecular
mass of the hydrocarbon is 78, what is its molecular formula?

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Reacting Masses and Volumes (of Solutions and Gases)

Candidates should be able to

(a) write and/or construct balanced equations.
(b) perform calculations, including use of the mole concept, involving reacting
masses (from formulae and equations); volumes of gases (e.g. in burning of
hydrocarbons); and volumes and concentrations of solutions.

In a balanced equation, the total number of the different atoms before and after
the reaction must be the same.

The relative amounts of the reactants and products (in moles) are indicated by the
coefficient in the balanced equation (also called stoichiometric coefficient).

Reacting Masses Excess reagents are those which are in excess of the stoichiometric amount required
for the reaction (as indicated by the balanced equation). They are not completely
consumed at the end of the reaction.

The limiting reagent is completely consumed at the end of the reaction and it
determines the yield of the reaction.

The theoretical yield is the maximum amount of a product that can be obtained in
a reaction from the given amounts of reactants.

The actual yield, however, may be much less due to incomplete reaction or product
loss during the reaction.

Percentage yield is a measure of the efficiency of the reaction.

actual yield
percentage yield 100
theoretical yield

Examples

Q1. What is the mass of Zn obtained when 50 g of ZnO is reduced by 50 g of charcoal?

Q2. Calculate the percentage yield when 31 g of methyl salicylate are obtained from 50 g of salicylic acid
and an equimolar amount of methanol.
The equation for the reaction is:
C7H6O3 + CH3OH C8H8O3 + H2O
salicylic acid methanol methyl salicylate

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 Atoms, Moles and Stoichiometry

Q3. To determine the sulphur content in tomato, 20.0 g of tomato were digested in concentrated nitric acid
and the SO42 ions produced were precipitated as BaSO4. 0.156 g of BaSO4 was collected. What was
the percentage, by mass, of sulphur in the tomato?

Q4. One brand of antacid chewing gum contains 2.5 % by mass of urea, NH 2CONH2. Given that urea reacts
with ethanoic acid (in vinegar) as follows:

NH2CONH2 + 2CH3CO2H + H2O CO2 + 2CH3CO2+NH4+

What mass of chewing gum is required to neutralise 1.00 g of ethanoic acid?

Volumes of Under similar conditions, equal volumes of gases contain equal number of molecules
Solutions and (Avogadro's Hypothesis).
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.
[NB. Standard temperature and pressure (s.t.p.) refers to 273 K and 1 atm pressure.
Room temperature and pressure (r.t.p.) refers to 292.5 K and 1 atm pressure.]

The concentration of an aqueous solution may be expressed either as

(a) mass of solute per dm 3 of solution (units: g dm3); or
(b) mol of solute per dm 3 of solution (units: mol dm3).

The number of moles (n) of a solute can be calculated from the relationship:

n = cV where c = concentration of solution in mol dm 3

V= volume of solution in dm3

When a given volume of solution is diluted, the number of moles of solute remains
unchanged after dilution.
i.e. no. of moles of solute before dilution = no. of moles of solute after dilution

c1V1 (original solution) = c2V2 (diluted solution)

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Examples

Q1. Calculate the volume of CO2 produced (at s.t.p.) by decomposing 15 g of CaCO3.

Q2. Calculate the volume of O2 that is needed to oxidise 20 dm 3 of NH3 to NO(g).

Q3. Phosgene, COCl2, is a poisonous gas. When inhaled, it reacts with water in the lungs to produce
hydrochloric acid which causes severe lung damage, leading ultimately to death. The chemical
equation is: COCl2 + H2O CO2 + 2HCl

Calculate the number of moles of HCl produced if 0.230 mol of COCl2 is mixed with 7.20 g of water.

Q4. Baking powder causes cakes to rise as a result of the reaction between cream of tartar (potassium
hydrogen tartrate, KHC4H4O6) and baking soda (NaHCO3).

KHC4H4O6 + NaHCO3 KNaC4H4O6 + CO2 + H2O

(a) What mass of cream of tartar is needed for the complete reaction of 1.00 g of baking soda?
(b) A sample of cheap self-raising flour contains 10.0 g of cream of tartar and 5.0 g of baking soda.
What volume of CO2 (at r.t.p.) would be released when the reaction between the two components
proceeds to completion?

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 Atoms, Moles and Stoichiometry

Q5. Calculate the concentration (in mol dm 3) of the solution obtained by dissolving 4.5 g of glucose,
C6H12O6, in water to make 250 cm3 of solution.

Q6. If 10.0 cm3 of a 3.00 mol dm3 sulphuric acid is diluted with water to give 250 cm 3, what is the
concentration of the diluted solution in mol dm 3 ?

Q7. Citric acid, C6H8O7, is a triprotic acid. The citric acid content of a 21.1 g sample of orange juice was
found to be completely neutralised by 23.50 cm 3 of 0.100 mol dm3 NaOH(aq). What is the percentage,
by mass, of citric acid in the sample?

Q8. 25.0 cm3 of a solution containing 15.00 g dm 3 of ethanedioic acid, (CO2H)2.xH2O, is completely
neutralised by 30.00 cm3 of a solution containing 3.40 g dm 3 of hydroxyl ions. Calculate the relative
molecular mass of the acid and hence, the value of x in the formula of the acid.

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 Atoms, Moles and Stoichiometry

Q9. 2.00 g of impure ammonium sulphate was dissolved in deionised water and made up to 250 cm 3 in a
volumetric flask. A 25.0 cm3 portion of this solution was boiled with 50.0 cm 3 of 0.100 mol dm3 sodium
hydroxide solution until no more ammonia gas was evolved. The excess sodium hydroxide in the
resulting solution required for neutralisation, 24.30 cm 3 of 0.100 mol dm3 hydrochloric acid. Calculate
the percentage purity of the sample.

Stoichiometric Candidates should be able to deduce stoichiometric relationships from calculations

Relationships involving reacting masses and volumes.

The stoichiometry of a chemical reaction is the relationship between the amounts of 1

reactant and the amounts of products in the reaction.

It is often shown by a balanced chemical equation.

Examples

Q1. An aqueous solution of NaOH contains 1.8 g of OH per dm3. 20.0 cm3 of it reacts
with 26.25 cm3 of 0.040 mol dm3 H3PO4 solution. How many moles of NaOH react
with 1 mol of H3PO4? Hence deduce the equation for the reaction.

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 Atoms, Moles and Stoichiometry

Q2. A solution contains 0.065 mol of a base M(OH)n per dm3. 25.0 cm3 of this solution
exactly neutralise 24.40 cm3 of a sulphuric acid containing 0.20 mol of hydrogen ions
per dm3. Calculate the number of moles of hydrogen ions which react with 1 mol of
the base M(OH)n. Hence, deduce the value of n and the equation of reaction.

Common Error A very common error made by candidates was to use 22.4 dm 3 instead of 24 dm3 as the
gas molar volume at room temperature.

Candidates were often inexact in their descriptions of the isotopic compositions of the
peaks in the mass spectrum (e.g. m/e = 18 could be either H216O or 18O).

Candidates attempted to formulate species corresponding to peaks in the mass

spectrum by using unusual isotopes (13C, 15N, 18O) or combinations of atoms at variance
with the molecular formula (e.g. C2H5O+ for m/e = 45 in the mass spectrum of ethanoic
acid, CH3CO2H).

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