Stoichiometric relationships 1 Flashcards
Simple molecular structures
Simple molecular structures consist of molecules not held to one another by formal bonds. The molecules themselves are constructed by means of covalent (shared electron pair) bonds between non-metal atoms
Molecular structures may normally be identified by their lack of metallic elements in the formula, however their are a few metal compounds that are covalently bonded and which consequently form simple molecular structures
Giant molecular strucutres
The whole network (lattice) is a construction of atoms all held together by formal covalent (shared electron pair) bonds. This effectively means that the structure is one giant molecule.
The smallest particle of each type of structure
atom, a molecule or an ion
The hydrogen standard
Hydrogen is the smallest atom and it was originally used as the standard by which all the other atoms were compared. It was assigned a value of 1 unit and other atoms masses calculated compared to hydrogen atoms.
The 1H isotope has a mass assigned a value of exactly 1 atomic mass unit. This was the original reference.
The carbon 12 standard
Nowadays the 12C isotope is used as a reference for comparison of relative atomic masses. This isotope has the assigned mass of 12.00000, all other atoms are measured relative to 12C.
Avogadros number
Avogadro’s number or constant is the number to which the mass of an atom must be multiplied to give a mass in grams numerically equal to its relative atomic mass.
Example:
Hydrogen has a relative atomic mass of 1 therefore 6.02 x 1023 hydrogen atoms have a mass of 1g
1 mole
The amount of any substance containing an Avogadro number of particles of that substance is called a mole.
1 mole of any substance has a mass equal to its relative mass expressed in grams
1 mole
The amount of any substance containing an Avogadro number of particles of that substance is called a mole.
1 mole of any substance has a mass equal to its relative mass expressed in grams
Example:
Example
1 mole of magnesium contains 6.02 x 1023 magnesium atoms
Simple atomic structurees
All of the atoms are held together by weak forces only. The substances are always gases at room temperature, liquifying and solidifying at temperatures far below zero celsius (0ºC). As the only known cases of simple atomic structure are the noble gases (Group 0), they are of little interest as regards moles calculations.
Simple molecular substances
1 mole of a simple molecular substance contains 1 mole of molecules of that substance = 6 x 1023 molecules
In the case of water, where 1 molecule is made up of two hydrogen atoms and 1 oxygen atom bonded together, it is clear that each molecule contains a total of three atoms. We can talk about these atoms as if they were not chemically bonded.
It is valid to say that 1 mole of water contains 2 moles of hydrogen atoms and 1 mole of oxygen atoms.
Giant molecular structures
These structures have a giant lattice in which the atoms are all covalently bonded together, effectively making the entire structure 1 molecule. The atoms may be all the same, in the case of a giant molecular element such as diamond, or they may be different as in silicon dioxide.
Giant ionic structures
Ionic compounds are giant structures comprising a lattice of oppositely charged ions. The simplest ratio of the ions is called the formula unit. 1 mole of an ionic compound is understood to contain 1 mole of formula units of that substance.
Giant metallic structures
Metallic structures comprise a giant structure of metal atoms within which the valence electrons are delocalised. In terms of discussing the number of moles the structure can be considered to be made up of associated atoms.
Composition by mass
The ratio of element mass within a compound depends on both the relative masses of the atoms involved as well as the number of them present. The ratio of atoms in water is 2:1, hydrogen to oxygen respectively.
However, as the mass of a hydrogen atom is 1 and the mass of an oxygen atom is 16, then the ratio in terms of mass is:
mass of 2 atoms of hydrogen = 2 x 1 = 2
to mass of 1 atom of oxygen = 1 x 16 = 16
The mass ratio of hydrogen to oxygen in water is always, 2 : 16
Valency
The valency of an atom is the number of single chemical bonds that it can make (in the case of a covalently bonding substance) or the number of electrical charges that it carries (for an ion). Notice that once again the nature of the substance in question requires that the definitions be adapted appropriately. The concept of valence can be used to find the formula of a compound from the valencies of its constituent elements, or to find the valency of an elements within a compound of known formula.
Every atom within a substance is assigned a valency number that is either positive or negative. The total sum of all of the valencies within a formula unit is zero.
Example: Find the valency of the chlorine atoms in the compound Cl2O7
The oxygen has a valency of -2
7 oxygen atoms make a total of -2 x 7 = -14
The overall valency must cancel out, i.e sum of the valencies of oxygen + sum of the valencies of chlorine = 0
Therefore Cl2 = +14
Valency of chlorine in Cl2O7 = +14/2 = +7
Covalent compounds
A covalent bond is a shared pair of electrons. When non-metals bond to other non-metals they always do so by sharing electron pairs. The total number of bonds that an atom has is called its valency.
In the water molecule oxygen combines with two hydrogens and so has a valency of 2.
The hydrogen atoms are each sharing one pair of electrons - they have a valency of 1. The oxygen atom is sharing two pairs of electrons - it has a valency of 2.
The rules of valency in compounds say that the total valency of the hydrogens must equal the valency of the oxygen.
i.e. 1 + 1 = 2
If the most electronegative element is assigned a negative valency and the most electropositive element a positive valency then the sum of the atoms’ valencies must equal zero.
Hydrogen (electropositive) = +1
Oxygen (electronegative = -2
Sum: [2 x (+1)] + [1 x (-2)] = 0
Ionic compounds
Ionic substances are made up of giant ionic lattices. The simplest formula unit consists of the simplest ratio of oppositely charged ions. The total electrical charge MUST equal zero in a neutral compound.
The valency of an ion is the number of electrical charges that it carries. A sodium ion has a single positive charge - it has a valency of +1. An oxide ion (from oxygen) has a charge of two minus, it has a valency of -2.Example: For the compound formed from sodium and oxygen.
The same valency rules apply as for the covalent substances. The sum of positives must equal the sum of negatives.
Sodium has a valency +1
Oxide (from oxygen) has a valency of -2
In order for the sum to equal zero we must have two sodium ions for each oxide ion.
The formula = Na2O
Using valencies
Once the valencies of a few elements are known it becomes a simple matter to construct the formula of unknown compounds using the valency method. Remember that the sum of the valencies of all of the atoms in the compound must equal zero.
Where an atom may have either positive or negative valency, it is negative if it is the more electronegative element in the compound and positive if not.
Example: From the water molecule above we know that the valency of hydrogen is +1.
If the valency of nitrogen in ammonia is -3 then we can construct the formula of ammonia thus:
We need enough hydrogens to cancel out the -3 valency of nitrogen. Each hydrogen = +1 therefore we need three hydrogen atoms.
The formula of ammonia = NH3
Working with ions
When using valencies to work out the formula of an ion we have to remember the final charge on the ion must equal the sum of the valencies, taking into account whether the valency of each atom is negative or positive.
Example: Find the formula of the sulfate (2-) ion given that the valency of the sulfur atom is +VI and the valency of the oxygen atom is -II
Oxygen always has negative valencies (unless bonded to fluorine)
There is one sulfur atom with a valency of +6 and overall the ion has a valency of -2
Therefore +6 +(xO) = -2
Therefore (xO) = -2 -6 = -8
each O =-2 therfore there are four oxgen atoms in the ion
Formula of the sulfate ion = SO42-
ionic compounds
Ionic compounds have positive ions arranged in a giant lattice with negative ions. Every positive ion is surrounded by negaitive ions and every negative ion is surrounded by positive ions. The overall structure has no charge, therefore the number of positive charges is exactly cancelled out by the number of negative charges. This is also the case in the simplest formula unit.
covalent compounds
In covalent compounds all of the atoms in each molecule are held to one another by bonds comprising electron pairs. In the case of double bonds there are two electron pairs involved in the bond. There are no full charges in covalent molecules unlike their ionic counterparts, but there may be partial charges caused by dipoles between atoms having different electronegativities, such as oxygen and hydrogen.
hydrated compounds
Ionic compounds in which water molecules has been used to build the crystal lattice (water of crystallisation) are called ‘hydrated’ salts
When many substances are crystallised from aqueous solution, water molecules form part of the crystal lattice and become an integral part of the final crystal structure. These molecules are called ‘water of crystallisation’ and when the compound is weighed out they must be taken into account.
Example: Cobalt(II) chloride crystals contain two molecules of water for every cobalt ion.
The formula of the crystals must be written CoCl2.2H2O showing the two water molecules.
Any mass of cobalt chloride weighed out also contains the water molecules.
Example: Calculate the mass of copper sulfate pentahydrate, CuSO4.5H2O, that must be weighed out to prepare 1dm3 of 1 molar solution.
The solution contains 1 x 1 = 1 mole of solute.
Relative formula mass = 63.5 + 32 + (4 x 16) + [5 x (2 + 16)] = 249.5
Therefore 249.5g must be weighed out.
Efflorescence
Certain hydrated compounds lose some of their water of crystallisation when left in the open air. This is known as efflorescence. A case in point is that of sodium carbonate decahydrate Na2CO3.10H2O. The crystals develop a powdery layer on the outside as water of crystallisation is lost to the atmosphere. Salts that effloresce cannot be used as standards for accurate preparation of solutions, as the exact composition of the crystals cannot be known.
Hygroscopy
Some compounds, typically ionic salts, absorb water from the atmosphere and increase in mass on exposure to air. Once again, the exact composition of the compound cannot be known and such salts cannot be used as primary standards. Sodium nitrate behaves in this way and, as such, is unsuitable for use in gunpowder, potassium nitrate being preferred instead.
Deliquescence
This is a special case of hygroscopy, where the salt ends up dissolving in the water absorbed from the air. A pellet of sodium hydroxide will turn into a small pool of sodium hydroxide solution when left in the air for long enough.
Percentage composition
The percentage composition of a material is generally taken to mean the percentage by mass of the elements within a substance.
Example: Calcium carbonate - CaCO3
The relative formula mass = 40 + 12 + (3x16) = 100
Calcium makes up 40 relative mass unit parts of this formula, therefore the percentage by mass of calcium is 40/100 = 40%
Carbon makes up 12 relative mass unit parts of this formula, therefore the percentage by mass of carbon is 12/100 = 12%
Oxygen makes up 48 relative mass unit parts of this formula, therefore the percentage by mass of oxygen is 48/100 = 48%
Empirical formula
The empirical formula is the simplest ratio of atoms within a chemical compound.
Example: Find the empirical formula of the compound which has the following percentage by mass composition: Carbon 12.12%; Oxygen 16.16%; Chlorine 71.17%.
Divide each percentage composition by mass by the relative atomic mass.
Carbon 12.12/12 = 1.01, Oxygen 16.16/16 = 1.01, Chlorine 71.17/35.5 = 2.00
These are in the approximate integer ratio 1xC : 1xO : 2xCl
Thus the empirical formula = COCl2
Example: Find the empirical formula of the compound which has the following percentage by mass composition: Carbon 12.12%; Oxygen 16.16%; Chlorine 71.17%.
Divide each percentage composition by mass by the relative atomic mass.
Carbon 12.12/12 = 1.01, Oxygen 16.16/16 = 1.01, Chlorine 71.17/35.5 = 2.00
These are in the approximate integer ratio 1xC : 1xO : 2xCl
Thus the empirical formula = COCl2
This method is used to calculate the empirical formula of unknown substances. If we also know the relative formula mass, obtainable from experimental data, then the molecular formula can also be found.
Example: 1.6 g of an unknown organic substance X was burned in excess oxygen and the mass of carbon dioxide produced determined by absorption in concentrated KOH solution.
The mass of water was determined by first passing the gases produced from the combusion through anhydrous calcium choride.
The following results were obtained:
Mass of carbon dioxide = 4.889g
Mass of water obtained = 2.405g
Mass of carbon in 4.889g CO2 = 4.889 x 12/44 = 1.333g
Mass of hydrogen in 2.405g of H2O = 2.405 x 2/18 = 0.267g
percentage by mass of carbon = 1.333/1.6 = 0.833 x 100 = 83.3%
percentage by mass of hydrogen = 0.267/1.6 = 0.167 x 100 = 16.7%
empirical formula = carbon 83.3/12 : hydrogen 16.7/1
empirical formula = C 6.94 : H 16.7
This simplifies to give an empirical formula of C5H12
Relative atomic mass
(abbreviated Ar)
Relative atomic mass is used to define the relative mass of one atom of a metallic element, or non-metallic element, which may be considered to consist of unique atoms for the purposes of calculations.
Note: Although sulfur and phosphorus contain discrete molecules (S8 and P4, respectively), they are usually treated in calculations as monatomic.
Relative molecular mass
(abbreviated Mr)
Relative molecular mass is used to define the relative mass of one molecule of a covalent substance, whether element or compound.
Note :The halogens bromine and iodine are liquid and solid respectively, at room temperature and pressure.
Relative formula mass
(abbreviated Mr)
Relative formula mass is used to define the mass of the simplest ratio of particles in ionic and giant covalent compounds.
The mole
The amount of substance that contains an Avogadro number of particles (6.02 x 1023) is called 1 mole of that substance. Where the word amount is used it always refers to the number of moles.
metals and other elements
Moles = mass / relative atomic mass
Simple covalent substances
Moles = mass / relative molecular mass
Ionic and giant covalent compounds
Moles = mass / relative formula mass
All of these relationships can be summarised as an equation triangle
Example 1: Calculate the number of moles in 12 g of magnesium
Magnesium has a relative atomic mass = 24
Moles of magnesium in 12 g = 12/24 = 0.5 moles
Example 2: Calculate the amount represented by 15g of silicon dioxide
Silicon dioxide, SiO2, is a macromolecular structure with a relative formula mass = 60
Moles of silicon dioxide in 15 g = 15/60 = 0.25 moles
Stoichiometry
The stoichiometry is shown by the relative coefficients of the components appearing in the chemical reaction.
Example
4NH3 + 5O2 4NO + 6H2O
The stoichoimetry of the reaction tells us that 4 molecules of ammonia react with 5 molecules of oxygen and produce 4 molecules of nitrogen monoxide and 6 molecules of water
1 mole is equivalent to 6.02 x 1023 molecules therefore the stoichiometry also gives us the ratio of moles reacting.
Consider the reaction:
Fe + S FeS
The stoichiometry of the equation shows us that one atom of iron is needed to react with each atom of sulfur. Extending this idea we can see that the same number of iron and sulfur atoms are always needed for a complete reaction.
Therefore the moles of iron are always equal to the moles of sulfur in this reaction.
If we are told the mass of iron that we start with is 5.6g then we can calculate the mass of sulfur needed. The calculation proceeds via the number of moles. [Relative atomic mass of Fe=56, S=32]
Moles of iron = mass /RAM = 5.6/56 = 0.1 moles
Therefore moles of sulfur = 0.1 moles
RAM of sulfur = 32
Therefore mass of sulfur needed = moles x RAM = 0.1 x 32 = 3.2g
The procedure followed is:
Example: Calculate the mass of chlorine needed to completely react with 2.24g of iron [relative atomic masses Fe=56, Cl=35.5]
2Fe + 3Cl2 2FeCl3
Mass of iron = 2.24g, therefore moles of iron = 2.24/56 = 0.04 moles
from the equation stoichiometry it can be seen that 2 moles of iron react with 3 moles of chlorine
therefore 0.04 moles iron react with 0.04 x 3/2 moles chlorine molecules = 0.06 moles
realtive molecular mass of Cl2 = 2 x 35.5 = 71
therefore 0.06 moles of chlorine = 0.06 x 71 = 4.26g
Word equation
Word equations simply show the names of the reacting chemical and products. They are of limited use except for giving an overall description of the chemical reaction. They give no indication of the relative amounts of the reactants or products involved.
Sodium hydroxide + sulfuric acid sodium sulfate + water
To make equations useful, they must show the individual formulae of the reactants and products and indicate the relative quantities in which they react. These ‘formula equations’ are dealt with below.
A chemical reaction is described according to the substance or substances that are present at the beginning - the reactants, and the substances that are present having been formed in the process at the end of the reaction - the products.
Traditionally, the transition in time between the reactants and the products is shown using an arrow. The arrow is NOT an equals sign, but rather an indication that the process takes place over a period of time.
Word equations show the names of the reacting species on the left hand side, and the products of the reaction on the right hand side, both sides linked by an arrow to indicate that change has occurred.
Reactants Products
The reactants and the products are described by their names. These equations give no indication as to the relative masses or numbers of moles reacting and produced and, consequently, they are of limited, or no use in calculations.
Examples:
Sodium hydroxide + nitric acid sodium nitrate + water
sulfuric acid + sodium chloride sodium hydrogen sulfate + hydrogen chloride
Calcium hydroxide + ammonium chloride ammonia + calcium chloride + water
Reaction types - Inorganic
The basic reactions of inorganic chemistry can be summarised as:
Synthesis Decomposition Neutralisation Precipitation Displacement Redox
Synthesis
Two simple substances, usually elements, combine to form a more complex compound. For example, the reaction between iron and sulfur.
Example: Synthesis of iron(II) sulfide
iron + sulfur iron(II) sulfide
The term may also be applied to more complex reactions which are designed to manufacture a specific compound, such as a pharmaceutical. In organic chemistry, for example, we may talk about aspirin synthesis:
Example: Synthesis of aspirin
ethanoic anhydride + 2-hydroxy benzene carboxylic acid aspirin + ethanoic acid
Synthesis is a rather general term that can be applied to almost any chemical change and as such, not very meaningful.
Example: Synthesis of ammonia
nitrogen + hydrogen ammonia
decomposition
Decomposition is when a compound is broken down, usually by heat, to produce simpler substances. An example is the thermal decomposition of calcium carbonate, producing calcium oxide and carbon dioxide.
Example: Thermal decomposition of calcium carbonate
calcium carbonate calcium oxide + carbon dioxide
neutralisation
Neutralisation is possibly the most common type of reaction encountered in schools. It is easy to carry out, there are many examples from everyday sources and it is easy to demonstrate using pH or litmus indicator papers. Acids occur in many foods such as fruits (lemons, oranges, apples, etc) vegetables (rhubarb), vinegar, etc.. Stomach acid is a reasonably strong solution of hydrochloric acid.
Neutralisation is the reaction of an acid and a base producing a salt and water. For example, the neutralisation of sulfuric acid by sodium hydroxide.
Example: Neutralisation of sulfuric acid by sodium hydroxide
sulfuric acid + sodium hydroxide sodium sulfate + water
Neutralisation can be extended to any compound that react with acids neutralising them. Such substances are called bases.
precipitation
ain and snow falls from the sky because the atmosphere cannot support the mass of particles accumulating together. Substances ‘fall out’ of solution because the water cannot dissolve them.
Precipitation (called double decomposition in old text books) is a reaction where two ionic solutions are mixed together, bringing ions that form an insoluble substance in contact with one another. Once the insoluble ionic compound is formed it falls out of the solution as a precipitate.
positive ion (aq) + negative ion (aq) insoluble salt precipitate (s)
Much use is made of this type of reaction in ‘wet’ analysis of inorganic ions, such as the use of silver nitrate solution to test for the presence of chloride ions. A white precipitate of silver chloride appears from the solution of the suspected chloride on addition of silver nitrate solution.
Displacement
Displacement reactions occur in several areas of chemistry.
Displacement of a weak (or volatile) acid from its salt by a stronger acid.
Displacement of a weak (or volatile) base from its salt by a stronger base.
Displacement of a metal ion from its compound by a more reactive metal (this is also a redox reaction)
Displacement of hydrogen gas from water or acids by reactive metals (this is also redox)
Example: Displacement of nitric acid from potassium nitrate
potassium nitrate + sulfuric acid potassium hydrogen sulfate + nitric acid
Example: Displacement of ammonia from ammonium chloride
ammonium chloride + calcium hydroxide calcium chloride + ammonia + water
Example: Displacement of copper from copper(II) sulfate solution
copper(II) sulfate + zinc zinc sulfate + copper
Example: Displacement of hydrogen gas from water by calcium metal
calcium + water calcium hydroxide + hydrogen
Redox
Redox is short for Reduction and Oxidation.
These are reactions that involve a transfer of electrons from one species (the reducing agent) to another species (the oxidising agent). The terms used are wonderfully confusing as the reducing agent gets oxidised and the oxidising agent gets reduced during the course of the reaction. Extraction of metals falls into this category, as the metal ions in the metal ore need electrons to become metal atoms. For example, the following reaction occurs in the extraction of iron from its ore, haematite.
Example: The extraction of iron (blast furnace)
iron(III) oxide + carbon iron + carbon monoxide
In this equation the iron 3+ ions get reduced by gaining three electrons from the carbon to become iron atoms.
Fe3+(aq) Fe(s)
For a full treatment of reduction and oxidation see ‘Colourful Solutions 8 - Reduction and Oxidation’.
Thermal stability
stability to heat is a relative issue. Enough heat will break even the strongest chemical bonds. Definitions of thermal stability usually depend on the method of heating being used. In general, a chemistry laboratory’s heat supply is provided by a Bunsen burner. If a compound is not decomposed by the hottest bunsen flame then we can say that it is thermally stable.
An example of the weakness of this definition is the case of iron(II) sulfate (green vitriol). This is generally considered to be thermally stable. However, this substance was known in the Middle Ages and used to make sulfuric acid (oil of vitriol) by heating strongly until decomposition. This produced sulfur trioxide (sulfur(VI) oxide) fumes. These fumes were lead into cold water giving the acid.
FeSO4 FeO + SO3
SO3 + H2O H2SO4
Hydrated compounds II
Hydrated compounds (compounds that contain water of crystallisation) also decompose when heated, losing some, or all, of their associated water molecules.
Example: Thermal decomposition of hydrated magnesium sulfate
magnesium sulfate heptahydrate Anhydrous magnesium sulfate + water
Some ionic compounds may undergo reaction between their water of crystallisation and the ions present, complicating this process. This is the case for magnesium chloride crystals, which decompose on heating to give a basic chloride salt containing chloride ions and hydroxide ions. This is not on the Syllabus.