Unit 1: Reaction Kinetics

Intro
Read Hebden p. 1

Endothermic Reaction Exothermic Reaction

Brick wall in text book is actually called activation energy.

Reaction Kinetics – the study of rates of rx. and the factors which affect the rates.
(note: “rxn” = reaction(s))

Expressing Rates

rate = quantity of a product formed or quantity of a reactant consumed

unit time unit time

in general: rate =  amount (a reactant or product) g/mol/L

 time s/min

eg.) Zn(s) + 2HCl(aq)  H2(g) + ZnCl2(aq)

r=  mass of Zn r =  [ HCl ] (note: [ ] = molar concentration)

 time  time

r =  volume H2
 time Do ex. 1-5 p.2 S.W. (SW is Hebden’s
Student Workbook)

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Calculations Involving Rxn Rates

use conversion factors to cancel units you don’t want and replace them with ones you do want!

Eg.) 0.020 mol = ? mol

min. s

Solution: 0.020 mol x 1 min = 3.3 x 10-4 mol

1 min 60 s s

Exactly 60s/1min, so don’t consider it

using significant digits. The 0.020 has 2
sig. digs., therefore the answer has 2.

You also must use molar mass to go grams  moles.

Eg.) 0.26 mol Zn = ? g of Zn

min s

Solution: 0.26 mol Zn x 65.4 g Zn x 1 min = 0.28 g of Zn

1 min 1 mol Zn 60 s s

You would use 22.4 L for conversions moles  L (STP) for gases.
1 mol

eg.) 0.030 mol O2 /s = L/s (STP)

Solution: 0.030 mol O2 x 22.4 L = 0.67 L O2

1s mol s
(The 0.030 has 2 sig digs so the answer must have 2 sig. digs.)
only used for gases at STP!

Practice:

The rate of a reaction is 0.034 g of Mg per second. Calculate the number of moles of Mg used
up in 6.0 minutes.

2
Comparing rates using balanced equations

ethane
2C2H6 + 7O2  4CO2 + 6H2O
consumed produced

eg.) ethane consumed at a rate of 0.066 mol /s, calculate rate of consumption of O2 in mol /s

Solution: 0.066 mol C2H6 x 7 mol O2 = 0.23 mol O2

s 2 mol C2H6 s

if ethane consumed at rate of 0.066 mol /s calculate rate of production of CO2

Solution: 0.066 mol C2H6 x 4 mol CO2 = 0.13 mol CO2

s 2 mol C2H6 s

- when other units used – you must use moles to (go over the “mole” bridge)
(you may go from L  L of one gas to another at STP)
eg.) given: 2Al + 3Br2  2AlBr3

if 67.5 g of Al are consumed per second - calculate the rate of consumption of Br2 in g/s.

Solution: 67.5 g Al x 1 mol Al x 3 mol Br2 x 159.8 g Br2 = 599 g Br2

s 27.0 g Al 2 mol Al 1 mol Br2 s

Eg) An experiment is done to determine the rate of the following reaction:

2Al(s) + 6 HCl (aq)  3 H2(g) + 2 AlCl3 (aq)

It is found that the rate of production of H2(g) is

0.060 g/s.

Calculate the mass of Aluminum reacted in 3.0

minutes.

3
Measuring Reaction Rates

eg. CaCO3(s) + 2HCl(aq)  H2O(l) + CO2(g) + CaCl2 (aq)

CO2 gas is
escaping
in an open system CO2(g) escapes
HCl(aq)

- as CO2 escapes, mass of the of the system will decrease

r =  mass of container and contents (open system)

 time
Note
rate = slope of amount. vs. time graph

Slope is negative if something is being consumed and positive if something is being produced.

Slope = rise (g)

run (s)

Mass of Rate = Slope (made +)

Container and
Contents (g)
rise (g)

run (s)

Time (s)

Note:
In reality, rate(slope) is changing over time,  rate is expressed over a certain interval
100. Average slope between 0 and 30s :
straight line drawn from “0” to time “30 s” .

Mass
(g)
To calculate rate at a certain point in time: it is
the slope of the tangent at that point.
20.

0.0 10. 20. 30.

Time (s)

4
 - Do demo with Cu & HNO3
discuss colour, mass, conc., pressure (volume) change
Monitoring Reaction Rates
[ do ex.6 on page 3 of SW.] [Read page 11 and do ex. 18-
19 on p. 11 SW.] [ do experiment on measuring rx. rates]

Which properties can be monitored (measured at specific time intervals) during a rxn in order to
determine rxn rate?

 ∆colour  ∆mass  ∆specific ions

 ∆Temperature  ∆Volume  ∆conductivity
 ∆pressure  ∆pH

1.) Colour changes

- only where coloured reactant is consumed or new coloured product formed.

eg1.) Cu(s) + 4HNO3(aq)  Cu(NO3)2(aq) + 2H2O(l) + 2NO2(g) + heat

copper clear blue clear brown

Could measure: intensity of blue

intensity of brown gas rate =  colour intensity
 time
- colour intensity measured using a spectrophotometer
(see p. 4 S.W.)

2.) Temp changes

- in exothermic rxn, temp of surroundings will increase rate =  temp

- in endothermic rxn, temp of surroundings will decrease  time
- measured in insulated container (calorimeter)

3.) Pressure changes (closed constant volume container)

- If more moles of gas (coefficient) in products pressure will increase.

Zn(s) + 2HCl(aq)  H2(g) + ZnCl2(aq) O m.o.g. < 1 m.o.g.

- If more MOG in reactants - pressure will decrease

rate =  pressure
- If equal MOG, pressure will not change:  time

NO2(g) + CO(g)  CO2(g) + NO(g)

2 m.o.g. 2 m.o.g.

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 4.) Mass changes

eg1) If only one solid is used up, you could remove periodically and weigh it:

Mg(s) + 2HCl(aq)  H2(g) + MgCl2(aq)

periodically remove
Mg and note the as H2 gas escapes, mass of
decrease in mass the container and contents
decrease.

rate =  mass of container & contents

 time

(read p. 4-5 SW. Ex. 7-9 page 5)

- Do Hand-In Assignment on Reaction Rates
- Do expt 18-B (or A) To look at factors affecting rx
rates.
Factors affecting
reaction rates

1.) Temperature - as temp increases rate increases

2.) Concentration of reactants

- as conc. of one or more reactants increases, rate increases

conc of a gas = partial pressure of a gas

(the pressure exerted by that gas in a mixture of gases)

3.) Pressure - affects rxns that have gases in reactants.

eg.) C(s) + O2(g) ---> CO2(g)

- as pressure increases, rate increases

Note: a decrease in the volume of rxn container will increase the pressure ( and therefore rate)

WHY? 123: Increase

4.) Nature of reactants chance of collision & arxn

a) Bonds
_ -rate of rxn depends on how strong & how many bonds in reactants need to be broken.

_ in general covalent bonds are strong and slow to break.

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Many bonds have to be broken and many new bonds have to form.
 this rxn is slow at room temp

Eg.) H2(g) + Cl2(g)  2HCl(g)

Remember, adding a
H-H + Cl - Cl flame means your rxn
is NOT at room temp
covalent bonds slow at room temp.

5.) Catalysts

- substances which can be added to increase the rate of a rxn. without being consumed
itself.

Demo with H2O2 + MnO2

2H2O2(l)  2H2O(l) + O2(g) uncatalyzed - slow

2H2O2(l) MnO2 2H2O(l) + O2(g) catalyzed - fast

Inhibitors

- substances which can be added to decrease the rate of a rxn.

(can combine with a catalyst or a reactant & prevent it from reacting)
-eg. -poisons (cyanide) - organophosphates (diazinon)
-antibiotics
-antidepressants (serotonin uptake inhibitors)
-sunscreens

The factor which affects only heterogeneous rxns (more than one phase)
Homogeneous rxn - all reactants are in the same phase

6.a. Surface area

-when 2 different phases react, the rxn can only take place on the surface.

- ↑ surface area by cutting solid into smaller pieces (liquids in smaller droplets)

These "inside" surfaces

are added

Sliced (larger surface area) Powder (huge surface area!)

Chunk (small surface area) 7
 b. Phase (Comparing rxn rates)

In general:

Aqueous ions > gases or liquids > solids

2 exceptions:
-solids do not mix,
 heterogeneous
- Read pages 5-9 SW.
-immiscible liquids
- do ex. 12-14 SW. (page 8)

Some points
1.) Temperature affects rate of all reactions
2.) Pressure (or volume) affect reactions with gaseous reactants
3.) Concentration only affects aqueous or gaseous reactants
4.) Surface area - affects only heterogeneous reactions.

- do ex. 15-17 p. 9-10 SW. Pay close attention to the graphs in question 17!

Everyday situations which require control of reaction rate

Cooking - improves taste - increase surface area

- kills some bacteria -increase temperature
- if too hot causes burning and productions of carcinogens - catalyst (wood stoves etc)
(benzopyrenes) - to decrease combustion rate
Food preservation - water on fire -smothers it (decreases O2)
- lower temperature - cools it
- anti-oxidants (eg. ascorbic acid) - fire retardant - forest fires
- keep from O2 (sealing) - children's clothing
- preservatives (nitrates, nitrites) Think of more! - airplane fuels - when spilled

Industrial Processes
Body chemistry - produce product quickly
eg.) - metabolism eg.) - fiberglass uses catalyst (hardener)
- fever can destroy bacteria hardens fast but not too fast
- neurotransmitters - awareness, sleep etc. - glue - epoxy uses catalyst
-hormones - messengers (adrenaline, sex hormones) - contact cement fast
-catalysts - enzymes (digestive etc) - concrete - ceramics - paint
- aging - oxy- acetylene welding (must be very hot)
- oil refining
Fuels - sewage treatment uses microbes to speed up breakdown
- concentration of O2 important - slow down reactions.
- to increase combustion rate - increase [ O2 ] eg.) nitroglycerine - keep cool - if too warm explodes- keep cool
& dry

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Collision theory - explains rates on the molecular level

Basic idea: - before molecules can react, they must collide.

H2 + I2 2HI

first later later still

successful collision ( reaction )

Effect of concentration

low conc. both high conc. blue high conc. both

low conc. red

low chance higher chance very high chance

of collision of collision of collision
(slow rxn) (faster rxn) (much faster rxn)

Effect of temperature
Read page 12 SW.
when molecules move faster:
1) more collisions per unit time  faster rate Do Ex. 20-22 on
page 12 of SW
2) they collide with more kinetic energy.

Enthalpy (H) & enthalpy change ( )

Enthalpy:

the “heat content” of a substance

or
the total KE (moving) & PE (stored) of a substance at const. pressure.

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Chemists interested in enthalpy changes ( )

H+H
Enthalpy (H) Heat is released to surroundings.
Exothermic  H is negative (-)
H
H2

Reaction Proceeds

O + O

Enthalpy (H) H
Heat is absorbed from the surroundings.
O2 Endothermic  H is positive (+)

Reaction Proceeds

Showing Enthalpy (heat) in the rxn equation

1)  shown H2 + S ---> H2S  = - 20 KJ ( -ive  means exothermic)

beside 6C + 3H2 ---> C6H6  = + 83 KJ ( +ive  means endothermic)

2) Thermochemical eqns:
- “heat term” shown on left side of arrow - endothermic (“it uses up heat like a reactant”)

eg. CH3OH + 201KJ  C(s) + 2H2(g) + ½ O2(g)

-“heat term” shown on right side of arrow -exothermic ( “it gives off heat like a product”)

eg. S(g) + O2(g) ---> SO2(g) + 296 kJ

Read page 13-16 in SW. Do ex. 24-28 on page 16 of SW.

-now back to collision theory...

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 Kinetic Energy Distributions

A KINETIC ENERGY DISTRIBUTION

# of Molecules

Kinetic Energy
A few A large number A few
molecules are of molecules molecules are
SLOW have moving FAST
(low KE) “medium” KE. (high KE)

Note: When T is increased….average KE increases

 fewer slow molecules and more fast molecules

A Kinetic Energy Distribution at Two Temperatures

Curve at Lower Temperature (T 1)

Curve at Higher Temperature (T 2)

# of Molecules

Kinetic Energy
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NOTICE:

- At the higher T: less slow (low KE) molecules and more fast (high KE) molecules

- The curve is more spread out at the higher T.

Activation Energy (Ea)

one that results in a rxn
Activation Energy:

the min E needed in a collision before a rxn can take place.

--OR—
the min E colliding particles need in order to have a “successful collision”

NOTE: Activation Energy (Ea) is fixed by the nature of the reactants

Activation
Energy (Ea)
# of Molecules

Kinetic Energy

molecules which have

enough E to react (~ 1/10
or 1/15)

NOTE:
 on the graph above, only a small fraction of the molecs (~ 1/10 - 1/15) have enough E to
react  
it is a slow rxn

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If T is increased ...

Curve at Lower Temp. (T 1) Activation

Energy (Ea)
Number of Molecules

Curve at Higher Temp. (T2)

Kinetic Energy

At higher T : At lower temp T1 ,

a greater fraction of the molecules only these molecs
have KE which is ≥ he Ea. have enough E to At higher temp T2 ,
now about 1/5th to 1/6th of the react these additional
molec have enough KE to react molecs also have
enough E to react

Rule of thumb:
If the Ea (threshold) is near the tail of the curve then …
… an increase of10oCin T ≈ a double in rxn rate (ie. about twice the # of molecs have enougt KE to react)

Activation Energy
barrier is near the
“tail” of the curve

Curve at Lower Temp. (T 1)

Activation
Energy (Ea)
Number of Molecules

Curve at Temp. T1 + 10 oC

Kinetic Energy
Notice at temp T1 + 10oC
the # of molecs with enough
E to react is ~ DOUBLE 13
Note:
If Ea barrier is near the middle (or on left side) of the curve, the rxn is already fast
 an ↑ in T has a less drastic effect on the rxn rate.

Ea

Curve at T1
Number of Molecules

Curve at T1 + 10 oC

Kinetic Energy

Notice:
Ea is low
Areas under each curve (to right of Ea
barrier) are very similar
 when Ea is low, an ↑ in T has less effect.

Activation Energies (back to collision theory.....)

Potential and Kinetic energy during a collision

 atoms and molecules have electrons on the outside

 these outer electrons repel each other

 As colliding molecs approach, the repulsion slows them down

 KE decreases.

 As they push against the repulsive force, PE increases (like compressing a spring)


is converted to
Kinetic Energy Potential Energy

KE + PE = Total E (stays constant)

if one decreases
the other increases
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Potential Energy Diagram

Molecules form a temporary,

As molecules approach unstable species called the
each other, KE is ACTIVATED COMPLEX
converted to PE
Activated Complex rearranges to form
the PRODUCT molecules

Potential Product Molecules move

Energy REACTANTS apart and speed up. PE is
(kJ) converted to KE.
(High KE, Low PE)

PRODUCTS
(High KE, Low PE)

Progress of Reaction

 Think of EA as a “barrier” which must be overcome before the reaction can take place

 Colliding molecules that don’t have enough KE to convert to PE do not make it “over the
Activation Energy Barrier”
 It is an UNSUCCESSFUL collision
 There is NO rxn.
 The molecs just bounce off of each other unchanged.

Activated Complex: a very short-lived, unstable combination of reactant atoms that exists
before products are formed.

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 to make it over the Ea barrier &
have a successful collision
The Role of Temperature

- the T determines how many (what fraction of ) molecs will have E > Ea

At low temp, the diagrams (Kinetic energy distribution) show that only a small percentage of
the molecules had enough E to overcome the Activation Energy barrier.

At the higher temp, a greater percentage of the molecs have enough E to “make it over” the
Activation Energy barrier.

  the rxn is faster.

SUMMARY from the diagrams:

Increasing the T increases the fraction of molecules which have sufficient E to form the
Activated Complex (ie. sufficient E to “make it over” the activation energy barrier.)

this is one reason that an increase in T will increase the rate of rxn.

IMPORTANT: NOTICE that a ∆ in T does NOT change the PE diagram at all !!

Temp does NOT affect the Activation energy or the  !!

Hebden # 29 -32

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 Hebden # 29 -32
Collision Geometry (comparing alignment)

consider the rxn: A2 + B2  2AB:

E.g. 1)
A A + B B NO RXN

 E.g. 1collision has unfavourable alignment (need higher E for collision to be effective)

E.g. 2)
A B A B A B

+ +

A B A B A B

Reactant Molecules (A2 & B2) They collide and form The AC breaks
an ACTIVATED apart to form the
APPROACH EACH OTHER COMPLEX PRODUCTS
(A2B2) (2AB)

 In the collision of e.g. 2 above, the reactants have favourable alignment (less energy
needed for an effective collision)
  EA needed for e.g. 2 < EA needed for e.g. 1

Summary of Collision Theory so far:

For any successful collision there are 3 Requirements:

Hebden # 33 - 40
1.) - particles must collide
2.) - they must collide with sufficient energy > Ea
3.) - they need to have correct alignment) (to keep Ea as low as possible)

Ea and  for forward and reverse reactions

Reactants Products

 If products can attain EA then the reverse reaction is possible.

17
 ACTIVATED
Eg..) 2 00 COMPLEX
18 0
16 0
Potential 14 0
Energy
12 0
10 0
REACTANTS
80
Forward Reaction
60
40
PRODUCTS
20

Progress of Reaction

1) From the graph above, find:

Ea (fwd rx.) = _________kJ  (fwd rxn. ) = _________kJ

This fwd rxn is ______thermic

2. Considering reverse rxn:

Use a different color pen and draw arrows for and Ea for the reverse reaction.

Ea (rvs rxn.) = _________kJ  (rvs rxn ) = _________kJ

This rvs rxn is ______thermic

Hebden # 41 - 45

Reaction Mechanisms
“every long journey begins with a small step

Most reactions (other than simple 2 particle collisions eg. Ag+ + Cl- AgCl(s) )
take place in a series of simple steps

Reaction # of Reacting Particles Probability of Reaction

Occuring in a Single Step
5C2O42- + 2MnO4- + 16H+  23 0%

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Reaction Mechanism: the series (sequence) of steps by which a rxn takes place.

 cannot be determined by just looking at overall rxn.

 deduced through much study and research (up to years)
 you will not be asked to come up with mechanism from scratch.
 some mechanisms are known, many are yet to be discovered.

eg) overall rxn: 4HBr + O2  2H2O + 2Br2 5 reactant particles…..DOES

NOT take place in a single step

The Mechanism (determined from lots of research):

step 1: HBr + O2  HOOBr (found to be slow)

step 2: HBr + HOOBr  2HOBr (fast)

step 3: HOBr + HBr  H2O + Br2 (very fast)

Each step is called an “Elementary Process”

Rate Determining Step (RDS): the slowest step in the mechanism.

Notes:
 the overall rxn can never be faster than the RDS
 the only way to speed up an overall rxn is to speed up the RDS

eg.) in the rxn above, increasing [HBr] or [O2] would:

- speed up Step 1 (the RDS)
- and the overall rate.

BUT speeding up a fast step (not the RDS) will have NO EFFECT on the overall rate.
(ie. ↑ [HOOBr] or [HOBr] has no effect on rate)

Determining overall rxn given the steps (mechanism)

Simply cancel things which appear on both sides and add up what’s left.

eg.) 1.) HBr + O2  HOOBr

2.) HBr + HOOBr  2HOBr
3.) 2HBr + 2HOBr 2H2O + 2Br2
_____________________________________________________________________
overall rxn: 4HBr + O2  2H2O + 2Br2
_____________________________________________________________________

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 eg.) 1.) A + 2X  AX2
2.) AX2 + X  AX + X2
3.) AX + A  A2 + X
_____________________________________________________________________

overall rxn:____________________________________________

Question:
the following rxn occurs in a 3 step mechanism:

2A4+ + B+  2A3+ + B3+ this is the overall rxn

step 1: A4+ + C2+  C3+ + A3+

step 2: A4+ + C3+  C4+ + A3+

step 3: ? find step 3.

Another Example:

Consider the following rxn for the formation of HCl in the presence of light.

Cl2 + CHCl3  HCl + CCl4

The following is the proposed rxn mechanism:

Step 1: Cl2  Cl + Cl

Step 2:

Step 3: Cl + CCl3  CCl4

Determine Step 2 of the rxn mechanism.

Step 2: ________________________________________________________

Reaction intermediate
-a species (atom, molecule or ion) which is produced in one step and used up in a later step.
(appears on right & also lower on left)

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 eg.) For the mechanism:

1) HBr + O2  HOOBr
2) HBr + HOOBr  2HOBr
3) 2HBr + 2HOBr  2H2O + 2Br2

intermediates are ___ & ______________

Notes:

 an intermediate does not accumulate (like a product) because as soon as it is formed, it

gets used up again
 intermediates are not necessarily unstable (may last long)
 an activated complex(AC) is very unstable and short-lived. (doesn’t usually have real
bonds)
has very high PE….only a temporary arrangement
Hebden # 46 - 53

PE diagram for a Reaction Mechanism

AC (step 1)
see p. 26 SW AC (step 2)
see p.27 AC (step 3)
see p. 27

PE HOOBr

HOBr
HBr + O2

H2O + Br2
STEP 1 STEP 2 STEP 3

REACTION PROCEEDS

Notes:

 each “bump” is a step

 the higher the bump the greater Ea 
the slower the step
 the highest bump (measured from the reactants level) is the RDS
 ACs are at top of bumps, intermediates in middle “valleys”, products at the end
 the Ea for the fwd overall rxn. is the vertical distance from reactants level to top of
highest bump.

Label the RDS on the last diagram.

Draw an arrow label the following to show:
1) Ea (overall rxn) 2) Ea for Step 1. 3)  for the overall rxn

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NOTICE: Ea is the difference in energy between the reactants and the top of the highest peak.

PE

Ea (Overall Rx.)

REACTION PROCEEDS

Question: Given this PE Diagram: Hebden # 54 - 55

PE
(KJ)

80

70

60

50

Reaction Proceeds

1. This mechanism has steps 2. Ea for overall rx = kJ

3. Step is the RDS 4. Step is the fastest step.

5. The overall rx. is thermic 6.  = kJ

7.  for reverse rx. = kJ 8. Ea (reverse rx.) = kJ

9. RDS for reverse rx. is step

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Catalysts: how they work

- “to avoid a hill, build a TUNNEL “

catalyst- an introduced substance which produce an alternate mechanism with a lower Ea

PE DIAGRAM SHOWING UNCATALYZED AND THE CATALYZED RXN

2 00

PE 18 0
(kJ) 16 0
Uncatalyzed route
14 0 Ea (uncatalyzed rx.)
12 0 Catalyzed route

10 0
Ea (catalyzed rx.)
80
REACTANTS
60

40
PRODUCTS
20

Progress of Reaction

Notes

 the E required (Ea) is less with the catalyst

 at same T, more molecs can make it over the “barrier” so rxn rate increases

 catalyzed rxns usually involve more steps but the highest Ea (highest bump) in catalyzed
rxn is never as high as in the uncatalyzed reaction

(eg. lower standards for a pass, eg. 30% will let more students pass!)

 a catalyst NEVER changes the PE of reactants of products - only the route between
them. (no change in  )

 an uncatalyzed rxn still continues at its own slow rate when a catalyst is added.  both
reactions aer occurring.
(the uncatalyzed rxn is usually insignificant compared to catalyzed rate)

 if catalyst speeds up forward rxn, it also speeds-up (reduces Ea for) the reverse rxn.

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Compare the Activation Energies for the fwd and rvs uncatalyzed and catalyzed rxns:

PE DIAGRAM SHOWING UNCATALYZED AND CATALYZED RXNS

2 00

PE 18 0
(kJ) 16 0
Uncatalyzed route
14 0 Ea(f) (uncatalyzed )

12 0 Catalyzed route

10 0 Ea (r)
Ea(f) (catalyzed) (Uncatalyzed )
80
REACTANTS
60

40
PRODUCTS
20

Progress of Reaction
Ea (r)
(Catalyzed )

How Catalysts Work

1. May provide a surface whose spacing of atoms is just right to break a reactant molecule
and hold it for an attack from another reactant.

2. Helping to form an intermediate which can react more easily to form products.

eg.) 2H2O2(l)  2H2O(l) + O2(g) (very slow uncatalyzed)

Hebden # 56 – 61
-add some KI (I-) Demonstration
Read p. 34 – 36
Hebden # 62 - 63
Catalyzed Mechanism:
step 1) H2O2 + I- ---> H2O + OI- (The catalyst I- is put in.)
step 2) H2O2 + OI- ---> H2O + O2 + I- (The catalyst I- is regenerated.)
overall rx. 2H2O2 ---> 2H2O + O2

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