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Week 4 Physical Chemistry 2021

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0% found this document useful (0 votes)
18 views27 pages

Week 4 Physical Chemistry 2021

Uploaded by

yanelisajeke6
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PPTX, PDF, TXT or read online on Scribd
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WEEK 4 – CHEMICAL KINETICS

Rate of Reactions
• When it is cold, a lizard slows down
• Movement depends on chemical reactions in muscles
• At lower temperatures the rate of these reactions slows
• Imagine a rocket launch:
• If the fuel burns too slow the rocket never gets off the ground
• If the fuel burns too fast = an explosion
• Chemical reactions require varying lengths of time for completion depending on the
characteristics of the reactants and products and the conditions under which the
reaction is run.
• Many reactions are over in a fraction of a second, whereas others can take much
longer.
• The study of the rate, or speed, of a reaction has important applications and is
critical in all areas of chemistry.
Rate of reactions
• In the manufacturing of ammonia from nitrogen and
hydrogen, you may wish to know what conditions will help
the reaction proceed in a commercially feasible length of
time.
• Another reason for studying reaction rates is to understand
how chemical reactions occur.
• By noting how the rate of a reaction is affected by changing
conditions, you can sometimes learn the details of what is
happening at the molecular level.
Experimental determination of rate
• Measuring the volume of gas produced per unit time. Eg
when metals react with acids they produce H2 gas. Here
Rate α ΔP (rate proportional to change in pressure)
• In reactions where a precipitate is formed, the amount of
precipitate formed in a period of time can be used as a
measure of the reaction rate. Here Rate α[P]
• For some reactions, the change in colour can tells us if the
reaction is taking place or not and the change in intensity of
colour can give indication of the rate of the reaction. Here
Rate α Δ(intensity)
How do reactions occur – Collision Theory
• Particles must collide with each other. They cannot react if they are
apart.

• The molecules/particles must collide with at least a certain


minimum energy called activation energy(Ea). If they collide with
less than this, they will simply bounce apart without reacting.
• The reacting molecules must have the correct orientation with
respect to one another.
Collision Theory …
• When reacting molecules collide with enough energy and with correct
orientation, they form an activated complex or transition state. This is an
unstable, high energy intermediate, between reactant and products. The
activated complex may breakdown to reform the reactants or it may break
down to form products.
Why reaction rate falls with time
• Consider the reaction: A + BAB
• In order for the product AB to form, the reactant molecules,
A and B must first collide.
• The rate is directly proportional to the number of collisions
per second which in turn is proportional to the concentration
of the reactants.
• As the reaction progressed A and B are consumed and their
concentration falls, so the number of collisions decreases.
• If the number of collisions decreases, then fewer products
are formed per second and the reaction rate will decrease.
Change of reaction with time
Δ[ ]
𝑅𝑎𝑡𝑒= =𝑠𝑙𝑜𝑝𝑒𝑜𝑓 𝑔𝑟𝑎𝑝h
Δ𝑡
Factors affecting reaction rates

• 1. Nature of a the reaction


• 2. concentration(gasses and liquids)
• 3. Surface area
• 4. Temperature
• 5. Catalyst
Nature of the reactants
• The nature of some reactants is such that the reactions are
extremely fast whilst other are slow. Most of the reactions are
somewhere in between.
Effect of concentration on the rate
• Increasing the concentration, increases the probability of a
collision between reactant particles.
• The concentration of pure solids and liquids cannot be changed.
Effect of the surface area on the rate

• If a solid reactant or a solid catalyst is broken down into smaller


pieces the rate of reaction increases.
• The speed increase happens because smaller pieces of the same
mass of solid have a greater surface area compared to larger pieces
of the solid. Therefore, there is more chance that a reactant
particle will hit the solid surface and react.
Effect of temperature on the rate
• For particles to collide successfully they need to have a minimum
amount of energy to overcome the activation energy of a
reaction.
• As the temperature increases, more and more particles will have
energy greater than or equal to the activation energy resulting in
more successful collisions.
Effect of a catalyst on the rate
• A catalyst is substance that speeds up a chemical reaction without
being used up.
• A catalyst provides an alternative route for the reaction by lowering
its activation energy so more particles will have enough energy to
react.
Rate of Reaction
• Speed of chemical reaction is measured as a change in the amount of
some reactant or product per unit time.
• For the reaction: H2 (g) + I2 (g)  2 HI (g)
• We can measure the disappearance of reactants or the appearance of
products.
[H 2 ] [I 2 ]
Rate =  or 
• Disappearance of reactant t t
[HI]
• Appearance of product Rate =  1/2
t
• The concentration of HI
 increases at 2x the rate of that

I2 or H2 decreases 
• For the overall rate to have the same value when
defined with respect to any reactant the change in HI must be multiplied
by 1/2
Rate Law
• Rates of reaction often depend on the concentration of one or
more reactants
• Consider a simple reaction A  products
• We can express this relationship in a Rate Law

• Rate = k [A]x
• Where k is a proportionality constant called a rate constant
and n is the reaction order
• The value of x determines how the rate depends on the
concentration of the reactant
Reaction rate expression or rate law
• The reaction rate expression is usually called the rate law.
• Experimentally, it has been found that a reaction rate depends on
the concentrations of certain reactants as well as the concentration
of catalyst.
• Consider the following reaction: aA+bB +cC…Products
• or
• The exponents X, Y and Z are often simple whole numbers 0,1 or 2.
An exponent 3 is known to occur in a very small number of
reactions but exponents >3 do not occur.
Order of reaction
• For the reaction with the following rate law:
• The exponent X is called the order of reaction with respect to A.
• Similarly with Y and Z which are order of reaction with respect to B
and C respectively.
• The value of “orders” determine how the rate depends on the
concentration of the respective reactants
• The sum of the individual exponents is called the overall order of the
reaction.
• The only way to determine the order of reaction is by carrying out
necessary experiments.
Zero Order Reactions

• Reactions whose rate does not depend upon the


concentration of the reactants.
• The rate henceforth is fixed and is determined by the rate
constant only.
• Eg. NH3(g) N2(g) + H2(g)
• No matter how much you change the concentration of
ammonia, the rate is fixed.
• Rate=k[NH3(g)]0 =k
First Order Reactions

• Reactions whose rate depends directly upon the


concentration of the reactants.
• The rate increases by n times if the concentration is
increased by n times.
• Eg. 2NO2(g) N2(g) + 2O2(g)
• If you double the concentration of NO2, the rate doubles.
• Rate=k[N2O(g)]1
Second Order Reactions
• Reactions whose rate depends directly upon the square of
the concentration of the reactants.
• The rate increases by n² times if the concentration is
increased by n times.
• Eg. CH3CHO(g) CH4(g)+CO(g)
• If you double the concentration of CH3CHO(g), then the rate
increases by four times. If you triple the concentration, the
rate increases by nine times, and so on.
• Rate=k[CH3CHO(g)]2
Rate Law
• Rate = k [A]x
• You cannot predict reaction order from the balanced equation.
Reaction order comes from experimental data.

Value of x Reaction order rate

0 zero Independent of the [A]

1 first Directly proportional to [A]

2 second Proportional to [A]2


The Rate Constant, k
• The size of k is related to the size of the activation energy, Ea.
The larger the value of Ea the smaller the value of k and vice
versa.
• The units of k depend on the overall order of the reaction.
Unit= mol1−order dm−3(1−order) time−1
• The rate constant is only constant at a given temperature.
• If the temperature is increased, then the value of the rate
constant increase in accordance with the Arrhenius equation.
Using experimental data to determine the rate law
Consider the reaction: A + B + C Products
EXP [A]/ [B]/ [C]/ Initial 𝑅𝑎𝑡𝑒 4 [ 𝐴 4] [ 𝐵 4] [𝐶 4]
mol.dm-3 mol.dm-3 mol.dm-3 rate/mol.d =𝑘 4/𝑘 1 ¿
m-3 𝑅𝑎𝑡𝑒 1 [ 𝐴1] [ 𝐵1] 𝐶1¿

1
2
1
2
1
1
1
1
3
6
3
3
=
[][][]
1
1
𝑥
1
1
𝑦
2
1
𝑧

3 1 2 1 12 1= ( 2 ) 𝑧

4 1 1 2 3 𝑧 =0 𝑤𝑟𝑡 𝑐
𝑅𝑎𝑡𝑒2 [ 𝐴2] [ 𝐵 2] [𝐶 2] 𝑅𝑎𝑡𝑒3 [ 𝐴3] [ 𝐵 3] [𝐶3]
=𝑘 2/𝑘1 ¿ =𝑘3/𝑘1 ¿
𝑅𝑎𝑡𝑒1 [ 𝐴1] [ 𝐵 1] 𝐶1¿ 𝑅𝑎𝑡𝑒1 [ 𝐴1] [ 𝐵 1] 𝐶 1¿
6
3
=
2
1 [][][]
𝑥
1
1
𝑦
1
1
𝑧
12
3 [][][]
=
1
1
𝑥
2
1
𝑦
1
1
𝑧

2 =( 2 ) 𝑥 4 =( 2 ) 𝑦
𝑥=1 𝑤𝑟𝑡 𝐴 𝑦 =2 𝑤𝑟𝑡 𝐵
In a kinetic study of the reaction 2NO(g) + O2(g)  2NO2(g), the following data were
obtained for the initial rates of disappearance of NO: (a) Obtain the rate law. (b) What is
the value of the rate constant?
Trial [A] [B] Rate 𝑅𝑎𝑡𝑒2
=𝑘 2/𝑘1 [ 𝐴 2/ 𝐴1 ] 𝑥 [ 𝐵2 / 𝐵1 ] 𝑦
1 0.1 0.1 2x 10-3 𝑅𝑎𝑡𝑒1
2 0.1 0.3 54 x10-3
3 0.15 0.1 4.5 x10-3 54 𝑥 10 −3
2 𝑥 10 −3
= ( )( )
0.1
0.1
𝑥
0.3
0.1
𝑦
𝑅𝑎𝑡𝑒3
=(𝑘 3/𝑘 1) [ 𝐴3 / 𝐴1 ] 𝑥 [ 𝐵 3/ 𝐵 1 ] 𝑦
𝑅𝑎𝑡𝑒1 27=3 𝑦 3 3=3 𝑦

2 𝑥 10 −3
= ( )( )
4.5 𝑥 10 − 3 0.15
0.1
𝑥
0.1
0.1
𝑦 𝑦 =3 𝑤𝑟𝑡 𝑡𝑜 𝐵
𝑅𝑎𝑡 𝑒𝑙𝑎𝑤=𝑘 [ 𝐴 ] 2 [ 𝐵 ] 3
=( ) 𝑥 3 2= 3 𝑥
2 (2) (2)
9 3
2.25=1.5 x
4
𝑘= 𝑅𝑎𝑡𝑒/ [ 𝑁𝑂 ] 2 [ 𝑂2 ] 3
𝑥=2 𝑤𝑟𝑡 𝐴 =200 units
The initial rate of a reaction A + B + C --------- Products was measured for
several different starting concentrations of A, B and C, with results given below
a. From these data, obtain the reaction orders with respect to A, B,
and C. b Then find the rate constant.
[A] mol/L [B] mol/L [C] mol/L Rate(mol
/(L.s))
𝑅𝑎𝑡𝑒 4
𝑅𝑎𝑡𝑒 1
=𝑘
[ ]
𝐶4
𝐶1
𝑧
EXP .1 0.03 0.03 0.0015 3.45 x10-6
EXP.2 0.06 0.03 0.0015 6.90 x10-6 3.45 𝑥 10 −6 0.003
=( )𝑧
EXP.3 0.03 0.06 0.0015 6.90 x10-6 3.45 𝑥 10 −6 0.0015
EXP.4 0.03 0.03 0.003 3.45 x10-6
1=2 𝑧
𝑅𝑎𝑡𝑒 2
𝑅𝑎𝑡𝑒 1
=𝑘
[ ]
𝐴2
𝐴1
𝑥 𝑅𝑎𝑡𝑒 3
𝑅𝑎𝑡𝑒 1
=𝑘
𝐵3
𝐵1
𝑦
[ ] 𝑧 =0 𝑤𝑟𝑡 𝑡𝑜 𝐶
6.90 𝑥 10 −6 0.06
=( )𝑥 6.90 𝑥 10 −6 0.06 [C]0=k[A][B]
3.45 𝑥 10 −6 0.03 =( )𝑦
3.45 𝑥 10 −6 0.03
2=2 𝑥
2=2 𝑦
𝑥=1 𝑤𝑟𝑡 𝐴
𝑦 =1 𝑤𝑟𝑡 𝐵

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