Week 4 Physical Chemistry 2021
Week 4 Physical Chemistry 2021
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.
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
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