Unit 3.5 - Chemical Kinetics Flashcards
Equation for the rate of a reaction
Rate of reaction = change in concentration/unit time
Unit of rate if measuring change in concentration over time
moldm-3s-1
Unit of rate if measuring change in volume over time
cms-1
Unit of rate if measuring change in mass over time
gs-1
Relationship between concentration and rate
Directly proportional
What does it mean that concentration is directly proportional to rate?
Double concentration = double rate
Which word do we always use when explaining rates
Time
How do we measure the rate of reaction for a change in concentration of reagent or product
By kinetic experiments
The change in concentration of what do we measure for the rate of a reaction?
Concentration of reagents or reactants
What’s the problem with measuring the rate of reaction through the change in concentration and what is done therefore?
Not always easy to follow the change in concentration
Usually another property that changes during the reaction is measured
How can we measure the rate of reaction at any instant in a reaction?
If continuous results are recorded, or many results over time, a graph is drawn
Th rate at any instant is measured using a tangent and a gradient at that point
What do we do to calculate the initial rate of a reaction?
Tangent at time = 0
How do we calculate the instantaneous rate of a reaction?
Tangent at that specific time and gradient
When is the rate of a reaction highest?
At the start of the reaction
Why is the rate of a reaction highest at the start of the reaction?
This is when there are the most reactants available for collision
List the things that he rate of a reaction is dependent on
Concentration
Pressure (for gas)
Temperature
Particle size
Catalysts
Light (sometimes)
What is the state that an element has to be in for it to be affected by pressure changes?
Gaseous
What does increasing the concentration or pressure (for a gas) do to the rate of reaction and why?
Increases the rate
Less distance between molecules in a given volume = increased number of collisions per unit time
What does a different particle size do to the rate of reaction? Explain
Smaller = increased rate
Increased surface area = closer together = more collisions per unit time
How do we measure the rate of a reaction?
We need to work out how much reactant has been used up or how much product has been produced
What properties can change with time that we can use to measure the rate of reaction?
Concentration of reactants or products
Mass of reactant
Volume or pressure of gas produced
pH
Colour change (or other electromagnetic absorption)
How do we work out the means of following a reaction?
Study the equation
Means of following this reaction:
CaCO3 + 2HCl —> CaCl2 + H2O + CO2
- Gas syringe to measure the change in volume over time
- Measure change in mass over time with scales (CO2 is a heavy gas)
What property about CO2 makes it useful for following the rate of a reaction? Explain
CO2 is a heavy gas
Can measure the change in mass over time with scales to measure the rate of the reaction
Means of following this reaction:
CH3CO2C2H5 + H2O —> CH3COOH + C2H5OH
- Measure change in pH over time (ethanoic acid is involved)
- Sampling and quenching
Means of following this reaction:
CH3COCH3 + I2 —> CH3COCH2 + HI
Measure change in colour over time using a colorimeter
(Brown solution of I2 disappears during the reaction)
Describe I2
Brown solution
Means of following this reaction:
2KI + H2O2 + 2H+ —> I2 + 2H2O
- Monitor change in pH over time
- Iodine-clock reaction - measure change in colour over time using a colorimeter
Example of a spectroscopic method to follow the rate of a reaction
NMR has been used to study the rates at which drugs act within the body
What type of method is using NMR to study the rate of a reaction?
Spectroscopic
When is the iodine-clock technique used to measure the rate of reaction?
In a reaction where iodine is produced
Give a description of the theory behind the iodine-clock reaction
Iodine ions can be oxidised to iodine at a measurable rate
Iodine gives a strongly coloured blue/black complex with starch solution
If a given amount of thiosulfate ion (with which iodine reacts very rapidly with to reform iodide ions) is added, the solution will be colourless until enough iodine has been formed to react with all of the thiosulfate
The time taken for this to occur acts like a clock to measure the rate of iodide ions being oxidised
What are iodide ions oxidised to at a measurable rate?
Iodine
In what solution does iodine give a strongly coloured blue/black complex?
Starch solution
Colour of iodine in starch
Blue/black
Iodine indicator
Starch
What does iodine do with thiosulfate ions?
Reforms iodide ions
When is the solution colourless during the iodine clock reaction?
When the iodine is reacting rapidly with the thiosulfate ions to reform iodide ions - it’s colourless until enough iodine has been formed to react with all of the thiosulfate
The rate of what is essentially being measured during the iodine-clock reaction?
The rate of iodide ions being oxidised
When does the indicator remain colourless during the iodine clock reaction?
When the thiosulfate reacts with the iodine, the indicator remains colourless
At which point does the iodine in the reaction mixture and the starch turn blue black during the iodine clock reaction?
The instant the last thiosulfate ion has reacted, there is iodine in the reaction mixture and the starch turns blue/black
Thiosulfate ion
S2O32-
How could reaction rates be compared using the iodine clock reaction?
If the amount of thiosulfate is kept constant, can compare the times taken to change colour
Suitable example of the iodine clock reaction
Oxidising iodide ions by hydrogen peroxide in acid solution
Equation for oxidising iodine ions by hydrogen peroxide in acid solution
H2O2 (aq) + 2H+ (aq) + 2I- (aq) —> 2H2O (l) + I2 (aq)
Equation for iodine reforming iodide ions with thiosulfate ions
I2 (aq) + 2s2O32- (aq) —> 2I- (aq) + S4O62- (aq)
Why is measuring the time taken to produce excess iodine in the iodine clock reaction only an approximation for the rate as the reaction proceeds?
The reaction is faster at first (higher concentration of reactant)
The average rate is measured
When is a reaction fastest and why?
At the start
Higher concentration of reactant
What gives a measure of the initial rate of reaction in the iodide clock experiment?
The time taken from mixing the reactant to the formation of the dark blue starch solution
What does the time taken from mixing the reactant to the formation of the dark blue starch solution in the iodine clock reaction give a measure of?
The initial rate of reaction
Initial rate equation
Initial rate ∝ 1/t
What is proportional to the reciprocal of time (1/t)?
initial rate
When does the beginning of the concentration-time curve approximate to a straight line in the iodine clock reaction?
If the amount of sodium thiosulfate used is small and is equivalent to m moldm^3 of iodine
Describe the beginning of the concentration time curve of a concentration of iodine against time graph
Straight line
How can we measure the rate of reaction of the isomerisation of cyclopropane to propane?
Can measure concentration over time using gas chromatography at a constant temperature
Under which condition must gas chromatography be done?
Constant temperature
Sampling
A process involving removing small samples of the reaction mixture at regular time intervals
Quenching
Where samples are placed in ice water to lower the concentration of the reactants and to stop the reaction continuing
How can the samples be tested after sampling and quenching?
Using other techniques like titration
What is sampling and quenching used to measure?
Changes in concentration
Why do we use ice water when sampling and quenching?
Cools the sample
Slows down the motion of particles (significantly - don’t actually stop completely)
Can monitor the exact concentrations at that moment in time
What can we titrate CH3CO2C2H5 with and what is the indicator?
NaOH
Methyl orange
What happens to the concentration of the product during the sampling and quenching method?
Concentration increases throughout the reaction
Starts to flatline when the reaction is stopping
What do we plot on a graph after sampling and quenching?
Concentration against time
What is the ratio between the moles of NaOH (titrant) and ethanoic acid produced during a sampling and quenching reaction example?
1:1
Advantages of quenching
Accurate
Easy to perform
No need for sophisticated equipment
Disadvantages of quenching
Laborious process (involves 5 titrations)
Equation for the reaction between 1-bromobutane and sodium hydroxide
CH3CH2CH2CH2Br + OH- —> CHCH2CH2CH2OH + Br-
What type of reaction is the reaction between 1-bromobutane and sodium hydroxide?
Nucleophillic substitution reaction
What does the fact that rate ∝ [OH-] in a reaction mean?
The rate of reaction depends on the concentration of OH-
If the concentration of OH- were doubled, the rate of reaction would double
Decomposition of hydrogen peroxide equation
2H2O2 —> 2H2O + O2
What is rate proportional to in the decomposition of hydrogen perioxide?
The concentration of the hydrogen peroxide
How can we form a rate equation?
By changing the proportionality sign for an equal sign and adding k, the rate constant
Rate equation for the decomposition of hydrogen peroxide
Rate = k[H2O2]
What does a rate equation give?
The dependence of the rate of the reaction on the concentration of the species in the rate equation
What is k in rate equations?
The rate constant
What is k (in rate equations) unique for?
Every set of chemical reactions
What is k (rate constant) independent of?
Concentration and time
What is the only thing that affects the value of k (rate constant)?
Temperature
What does the value of k (rate constant) depend on?
The reaction being studied
The temperature
What odes a higher k value mean?
Faster reaction
Example of a reaction with a high k value
Fireworks
Example of a reaction with a low k value
Rusting
How can the rate equations deduced?
From kinetic experiments
How can rate equations not be deduced?
From chemical equations
What does it mean if a reaction is first order with respect to something?
The rate of reaction depends on the concentration of that thing to the power one
What is the reaction 2H2O2 —> 2H2O + O2’s order with respect to hydrogen peroxide?
First order
How is the order of reaction found?
By experiment
How is the order of a reaction not found?
By chemical equations
General rate equation for a reaction whose rate depends on the concentration of reagents A and B
Rate = k[A]^x[B]^y
In Rate = k[A]^x[B]^y
What is x?
The order of the reaction with respect to A
In Rate = k[A]^x[B]^y
What is y?
The order of the reaction with respect to B
Order of reaction
The power to which the concentration term must be raised to fit the rate equation - is the exponent