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RATE AND EXTENT OF REACTION

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  RATE AND EXTENT OF REACTION

 Change in concentration of products/reactants per (unit) time.

 Change in amount/number of moles/volume/mass of products or reactants per (unit)
time.
 Rate of change in concentration/amount/number of moles/volume/mass.
 Amount/number of moles/volume/mass of products formed/reactants used per (unit)
time.
 Here we are checking how fast/slow did the change occurred.
 The change may be measured by mass, volume and concentration.

 UNITS:
o Change in concentration over time (mol·dm−3·s−1)
o Change in mass per unit time (g·s−1)
o Change in volume per unit time (dm3·s−1).
 The gradient of a concentration / mass / volume versus time graph gives the rate of a
reaction, thus a steeper gradient means a higher rate of reaction.

 EQUATIONS

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  COLLISION THEORY

 In order for a reaction to occur, molecules need to collide under specific conditions.

the conditions for successful collisions are:

 PARTICLES MUST COLLIDE WITH CORRECT ORIENTATION

 The structure of the molecules and their relative orientations to each other is
important for effective collisions.
 Some catalysts function by improving molecular orientation.

 PARTICLES MUST COLLIDE WITH SUFFICIENT ENERGY

 The molecules have to collide with sufficient amount of energy for bonds to break and
the reaction to occur (activation energy).

 MAXWELL-BOLTZMAN DISTRIBUTION CURVE

 The Maxwell-Boltzman distribution curve shows the distribution of the kinetic energy
of molecules.
 The area under the graph to the right of the activation energy line represents the
particles with sufficient kinetic energy.

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  HYPOTHESIS AND PREDICTION

 The hypothesis and prediction state what you believe will happen based on
background information.
 These statements can be both qualitative and quantitative.

 INDEPENDENT VARIABLE (EXPERIMENTAL VARIABLE)

 The independent variable is the factor changed by the person doing the experiment.
 This is the one you manipulate or vary during the experiment.

 DEPENDENT VARIABLE
 The dependent variable changes in response to the independent variable.
 It is the one that is measured by you during the process of the experiment.

 CONTROLLED VARIABLES

 Controlled variables are held constant so as not to directly affect the independent and
dependent variables.

 THE MOLE

Atoms, molecules and ions are too small to count, and there are so many particles in even the
smallest sample of a substance.
A mole of particles is an amount of 6,02 x 1023 particles (Avogadro’s number, NA.)

n=
 MOLAR MASS

 Particles are too small to weigh individually.

 Molar mass (M) is defined as the mass in grams of one mole of that substance (atoms,
molecules or formula units) and is measured in the unit g.mol-1.

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  CONCENTRATION

 The concentration of a solution is the number of moles of solute per unit volume of
solution.

 MOLAR VOLUMES OF GASES

 If different gases have the same volume under the same conditions of temperature and
pressure, they will have the same number of molecules.
 The molar volume of a gas, VM, is the volume occupied by one mole of the gas.
 VM for all gases at STP is 22.4 dm3·mol−1.
 Standard Temperature and Pressure (STP) is 273 K (0°C) and 1,01×105 Pa.

n=
 PERCENTAGE COMPOSITION

 Percentage composition of element = × 100

 PERCENTAGE PURITY
 Sometimes chemicals are not pure and one needs to calculate the percentage purity.
 Only the pure component of the substance will react.
 For an impure sample of a substance

 Percentage purity =

 STEPS TO DETERMINE THE PERCENTAGE PURITY

 Determine moles of products.

 From the balanced formula, determine the ratio between reactants and products.
 Using the ratio, determine the number of moles of reactants.
 Determine the mass of pure reactant.
 Calculate the percentage purity of the sample.

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  PERCENTAGE YIELD

 When you make a chemical in a laboratory a little of the chemical is always lost, due
to evaporation into the surrounding air, or due to a little being left in solution.
 Some of the reactants may not react.
 We say that the reaction has not run to completion.

 Percentage yield =

 STEPS TO DETERMINE THE PERCENTAGE YIELD

 Determine moles of reactants.

 From the balanced formula, determine the ratio between reactants and products.
 Using the ratio, determine the number of moles of products and convert to mass.
 Determine the theoretical mass of product.
 Calculate the percentage yield.

 Empirical formula to Molecular Formula

 The empirical formula is the simplest whole number ratio of atoms in a molecule.
 The molecular formula is actual ratio of the atoms in a molecule.
 The molecular formula can be calculated from the empirical formula and the relative
molecular mass.

 STEPS TO DETERMINE MOLECULAR FORMULA

 Determine the empirical formula (if not given):

o Determine the mass of the elements.
o Determine moles of each substance.
o Simplify the atomic ratio.
 Determine the molar mass of the empirical formula.
 Determine the ratio between molecular

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  LIMITING REACTANTS

 In a reaction between two substances, one reactant is likely to be used up completely

before the other.
 This limits the amount of product formed.

 The amount of limiting reactant will determine:

• The amount of product formed.

• The amount of other (excess) reactants used.

 Determining limiting reactants

o Calculate the number of moles of each reactant.

o Determine the ratio between reactants.
o Determine limiting reactant using the ratios.

 If one reactant is in excess, it means that there is more than enough of it.
 If there are only 2 reactants and one is in excess, it means that the other is the limiting
reactant.

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  FACTORS INFLUENCING REACTION RATE

 STATE OF DIVISION / SURFACE AREA

 Its applies when one of the reactants is a solid

 Surface area refers to the total number of reactive sites exposed for the reaction to
occur.
 The reactive site exposed is in line with correct orientation of reactants for enhancing
effective collision
 Increase state of division (powder instead of chunks) increases rate of reaction by
increasing effective orientations and surface area.
 There will be more effective collisions per unit time
 Hence, the rate of reaction increases.

KEY!
 Larger surface area/state of division.
 More particles (per volume) with correct orientation /.More contact points.
 More effective collisions per (unit) time.
 Hence rate of reaction increases.

 PRESSURE
 Its applicable to gases only
 In physics pressure is defined as the force per unit area.
 Increase pressure by decreasing volume, increases the concentration of the gas thus
increasing the rate of reaction
 According to collision theory: If the pressure in a system is increased; the distance
between the particles decreases, resulting in the increase of the number of particles
with the correct orientation.

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  The number of effective collisions increases, hence the rate of reaction increases.
 Also, if the pressure in a system is decreased; the distance between the particles
increases, resulting in the decrease of the number of particles with the correct
orientation.
 The number of effective collisions decreases, hence the rate of reaction decreases.

 CONCENTRATION

 Its applicable to gases and solutions only

 Concentration is defined as the number of particles per unit volume.
 The greater the concentration, the more particles are confined in a smaller space.
 This leads to more collisions, and subsequently more effective collisions.
 According to collision theory: If the concentration of reactants is increased; the
number of particles per unit volume increases, resulting in the increase of the number
of particles with the correct orientation.
 The number of effective collisions per unit time increases.
 Hence, the rate of reaction will increase.
 Also, if the concentration of reactants is decreased; the number of particles per unit
volume decreases, resulting in reduction of particles with the correct orientation.
 The number of effective collisions per unit time decreases.
 Hence, the rate of reaction will decrease.

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KEY!

o More particles per unit volume.

o More effective collisions per unit time / Higher frequency of effective collisions.
o Increase in reaction rate.

 TEMPERATURE

 Temperature is the measure of the average kinetic energy of molecules.

 When the temperature is increased, more particles have sufficient energy to overcome
the activation energy.

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  And more effective collisions can take place per unit time.
 Hence the rate of reaction increases.

KEY!

 curve b was obtained at a high temperature

 At a higher temperature particles move faster/have a higher kinetic energy.

 More molecules have enough/sufficient (kinetic) energy.
 More effective collisions per unit time/second./Increased frequency of effective
collisions.
 Reaction rate increases.

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  CATALYST

 A positive catalyst is a chemical substance that increases the rate of chemical reaction
without itself undergoing permanent change.
 The presence of a catalyst decreases the activation energy.
 The particles require less collision energy to undergo an effective collision.
 Leading to more effective collisions.
 Hence the rate of reaction increases.

 WHAT IS THE FUNCTION OF THE CATALYST IN THIS EXPERIMENT?

 Curve Y/it was obtained for the reaction where a catalyst was added.
 Speeds up the reaction.
 Increases the reaction rate.
 Provides alternate pathway.
 Lowers the (net) activation energy.
 It does not change the heat energy

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  NATURE OF REACTANTS

 The physical and chemical properties of certain molecules make them more likely to
react.
 FOR EXAMPLE:
o O2 has many effective orientations
o F’s electronegativity makes it more reactive
o Tertiary alcohols have limited effective orientations due to molecule structure
 ENERGY AND CHEMICAL CHANGE


 In a chemical reaction energy is used to break old bonds, and energy is released when
new bonds form.
 During a reaction energy of the system changes; and that change in energy is called
enthalpy change (heat of reaction)
 Enthalpy change is calculated using the following equation:

 Also in a reaction products are not formed directly, however an intermediate molecule
forms.
 This intermediate molecule is neither a reactant nor a product and is called Activated
Complex
 However, activated complex eventually breaks up to form products

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  An activated complex is defined as the molecule which is highly unstable, high
energy and it breaks up to form products.
 The potential energy of this activated complex is equal to the activation energy of the
reaction.
 There are two types of reactions as far as energy is concerned i.e.

 EXOTHERMIC REACTION

 Exothermic reaction is the reaction that releases energy

 Reactants absorb less energy than the energy that is produced
 Energy of reactants is greater that the energy of products
 the enthalpy change(heat of the reaction) of the reaction is negative
 also known as spontaneous reaction
 heat as product

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  ENDOTHERMIC REACTION.

 chemical reaction that require (absorbs) energy

 Reaction that absorbs more energy it produces
 Energy of reactants is less that the energy of products
 the enthalpy change (heat of the reaction) of the reaction is positive
 non-spontaneous reaction
 Heat as reactant

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  CHEMICAL EQUILIBRIUM

 OPEN SYSTEM

 An open system continuously interacts with its environment.

 This means some of the products may escape the reaction vessel as a result of that the
total mass of the system will decrease.
 This happens when one of the product is a gas and is not stored
 However, the mass lost by the system will be gained by surroundings.
 Hence, the law of conservation of mass is obeyed.
 Also, some reactants may come from surroundings to the system
 Effectively the mass of the system would increase, and then the mass of surrounding
would decrease.

 CLOSED SYSTEM

 A closed system is isolated from its surroundings and is one where no reactants or
products can leave or enter the system.
 This means neither reactants nor products may join or leave the system.
 A reaction is a reversible reaction when products can be converted back to reactants.
 Reversible reactions are represented with double arrows.
 Chemical equilibrium is a dynamic equilibrium when the rate of the forward
reaction equals the rate of the reverse reaction.
 Chemical equilibrium can only be achieved in a close system.

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  LE CHATELIER’S PRINCIPLE

 When an external stress (change in pressure, temperature or concentration) is

applied to a system in chemical equilibrium, the equilibrium point will change in
such a way as to counteract the stress.
 Equilibrium will shift to decrease any increase in concentration of either reactants or
products.
o Adding reactant: forward reaction favoured
o Adding product: reverse reaction favoured
o Equilibrium will shift to increase any decrease in concentration of either reactants or
products
o Removing reactant: reverse reaction favoured
o Removing product: forward reaction favoured
 The concentration can be changed by adding/ removing reactants/products that are in
solution (aq) or a gas (g).
 Changing the mass of pure solids (s) or volume of liquids (l) will not disrupt the
equilibrium or change the rate of the reactions.
 An increase in temperature increases the rate of both the forward and the
reverse reaction, but shifts the equilibrium position.
 NB: Temperature change is the only change that affects Kc.
 Equilibrium will shift to decrease any increase in pressure by favouring the reaction
direction that produces less molecules.
 Equilibrium will shift to increase any decrease in pressure by favouring the reaction
that produces more molecules.
 To identify the reaction direction, use the ratios in the balanced equation.

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  COMMON ION EFFECT
 When ionic substances are in solution, they form ions:
 If HCl is added to this solution, the concentration of Cl− ions will increase because Cl−
is a common ion.
 The system will attempt to re-establish equilibrium by favouring the reverse reaction,
forming a white sodium chloride precipitate.
 The disturbance of a system at equilibrium that occurs when the concentration of a
common ion is increased is known as the common ion effect.

 EQUILIBRIUM CONSTANT (KC)

 General equation: aA + bB → cC


 Where A,B,C are chemical substances (ONLY aq and g, NOT s or l )
 And a,b,c are molar ratio numbers
 Kc value is a ratio and therefore has no units.
 If Kc > 1 then equilibrium lies to the right – there are more products than reactants.
 If Kc < 1 then equilibrium lies to the left – there are more reactants than products.
 Kc values are constant at specific temperatures.
 If the temperature of the system changes then the Kc value will change.
 Calculate the value of the equilibrium constant for this reaction.

 EQUILIBRIUM CONSTANT TABLE

o Ratio: from the balanced equation

o I: Initial moles: This represents the starting amounts of reactant present in the system
before the reaction proceeds.
o C: Change in moles: This represents how much reactant is used up as well as how
much product is formed according to the mole ration of the reactants and products.
The number of moles decomposed.
o E: Equilibrium moles: This represents the final amount of reactant and product now
present at equilibrium. If this is in moles, then the equilibrium concentration needs to
be calculated from this for final calculation.

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  CATALYST AND EQUILIBRIUM

 When a catalyst is added, the rate of the forward as well as the reverse reaction is
increased.
 The use of a catalyst does not affect the equilibrium position or the Kc value at all, but
allows the reaction to reach equilibrium faster.

 BOTH the forward and revers/back reaction rates to increase.

 This means that the chemical equilibrium will be reached faster than without a
catalyst.
 In the graph above, it can be seen that when a catalyst is added, both forward and
reverse/back reactions increase simultaneously and then equilibrium is re-established
at the higher rate.

 EQUILIBRIUM SHIFT ACCORDING TO LE CHATELIER

o Identify the disturbance Adding/removing reactants or products, pressure change,
temperature change.
o State Le Chatelier’s principle
o system response
 Use up / create more products or reactants, make more/less gas molecules,
increase/decrease temperature.
o state favoured reaction
o discuss results
 Equilibrium shift, change in colour/concentration/ pressure/temperature.

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  IN INDUSTRY THE PRODUCT IS REMOVED AS QUICKLY AS IT FORMS.

 To favour the forward reaction/production.

 To increase the yield.
 Prevent the decomposition
 GRAPHS

 THE EFFECT OF INCREASE IN REACTANTS OF THE ABOVE REACTION

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  THE PRESSURE

 The pressure is inversely proportional to the volume from Boyle‘s law.

 If the pressure of the system is changed (by changing volume or amount of gas),
the sum of stoichiometric coefficients of both reactants and products will decide
the direction of equilibrium shifting.
 An increase in pressure forces the reaction at equilibrium to shift towards the side
with least moles.
 A decrease in pressure forces the reaction at equilibrium to shift towards the side
with most moles.

 A decrease in the pressure (by increasing the volume of the container) will cause
the reverse/back reaction to be favoured as to counteract the change in pressure,
the reaction must proceed to favour a greater number of moles of gas.

KEY!
 2A(g) + 3B(g) ⇌ 3C(g)

 When the pressure increases, the reaction that leads to a decrease in the number of
moles will be favoured.
 When the pressure increases, the yield increases because the equilibrium position
shifts to the right
 The concentration of both the reactants and products increase.
 The volume of the container is decreased.

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  THE EFFECT OF INCREASE IN TEMPERATURE

 Given the following hypothetical reaction equation

 A + B ⇌ C , ΔH < 0

 When considering the change in temperature, firstly the type of reaction must be
identified, whether it is endothermic or exothermic.
 This is because the heat is absorbed in an endothermic reaction, then released in an
exothermic reaction.
 What would happen in this reaction if temperature is decreased?
 Since the reaction has an enthalpy less than zero that means the forward reaction is
exothermic.
 Hence, by decreasing temperature of an exothermic reaction that will force the
reaction at equilibrium to shift towards (favours) products (C), then it will re-establish
equilibrium.
 Also, if temperature could be increased the reaction at equilibrium will shift towards
(favours) reactants (A and B).

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KEY!

 Percentage yield increases with an increase in temperature.

 Forward reaction is favoured.
 Increase in temperature favours an endothermic reaction.

 Temperature increases
 More products formed as forward reaction is favoured and reactants will decrease.
 KC will increase as there will be a larger numerator an a small denominator

OR

 More reactants will form as the reverse/back reaction is favoured and products will
decrease.
 KC will decrease as there is a smaller numerator and a larger denominator.

 Temperature decreases
 More reactants will form as the reverse/back reaction is favoured and products will
decrease.
 KC will decrease as there is a smaller numerator and a larger denominator.
OR
 More products formed as forward reaction is favoured and reactants will decrease.
 KC will increase as there will be a larger numerator and small denominator.

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