5.

1 Introduction to Thermochemistry

Thermochemistry - is the study of the _____________________ that accompany ________________ or

______________________ changes in matter.
(a) Physical (hydrogen boils at -252℃); H2 (l) + heat → H2 (g)
(b) Chemical (hydrogen burns ); 2H2 (g) + O2 (g) → 2H2O (l) + heat
(c) Nuclear (hydrogen undergoes nuclear fusion in the Sun, producing helium).

Energy – the ability to do ____________________.

 Potential energy: (i) chemical potential energy is the energy stored in ________________________
(ii) nuclear potential energy is due to __________________________________________________
 Kinetic energy: _________________, ____________________ and __________________________

First Law of Thermodynamics: ______________________________________________________________

For any system that ______________energy, the energy must _____________the surroundings; for any
system that ______________ energy, that energy must ____________ the surroundings.

Thermal Energy: _____________ of all the energy available from a substance as a result of the ___________ of
its particles (kinetic energy of all the particles)

Temperature (T)- the ___________________ kinetic energy of the particles in a sample, measured in °C or K

Heat (Q) - ______________ of energy that enters or leaves a substance (the amount transferred), measured in
Joules (J). Energy flows between substances because of their ________________ in temperature.

Enthaply (H)- ________________ internal energy of a substance at a constant pressure. Hard to measure
directly - - easily measure and study _________________________ in a reaction. The enthalpy change of a
process is equivalent to its ___________________________at constant pressure.

Open system – can exchange both ___________ and _____________ with its surroundings
Closed system – can exchange ___________ but not _____________ with its surroundings
Isolated system – cannot exchange ____________ or _______________ with its surroundings
Enthalpy Change -

Exothermic – reactants have a _________ Endothermic - reactants have a __________

potential energy. Potential energy of potential energy. Kinetic energy of
reactants is converted into _____________ surroundings is converted into ___________
energy, which _____________ the average energy, which _____________ the average
Types ofenergy
kinetic EnergyofChanges:
the surroundings kinetic energy of the surroundings
(temperature ____________________) (temperature of surrounding ____________)

1|Page Energy and Rates Unit

 Exothermic Endothermic

Energy is __________________ Energy is__________________

ΔH ____ O ΔH ____ O

Surroundings will __________________ up Surroundings will __________________ down

1. Physical Changes - _____________________ change in enthalpy (__________ of kJ/mol). Change in

_________________ forces between molecules as they change phase.

2. Chemical Changes - ___________________ change in enthalpy (______________ of kJ/mol). Change in

_________________ forces between molecules as reactants break apart to from products.

3. Nuclear Changes- _____________________ change in enthalpy (__________ of kJ/mol). Change in

________________________________ holding together the nucleus of an atom. Einstein: _____________ where
m-mass and c=speed of light (3.0 x 10-8m/s). A tiny mass is equivalent to a significant amount of energy.
 Nuclear Fission –

 Nuclear Fusion -

Enthalpy Diagrams in Thermodynamics:

 Show the net change in energy in a chemical reaction. A physical change has an enthalpy change in the
range of tens of kJ/mol, a chemical change is hundreds of kJ/mol and a nuclear reaction has an energy
change in the billions of kJ/mol

2|Page Energy and Rates Unit

 Bond Energies

Recall: the total chemical potential energy of a substance is the energy that is stored within the chemical bonds

 Breaking these chemical bonds requires energy, whereas forming chemical bonds releases energy
 The difference in the bond energies of reactants and products can be used to estimate the change in enthalpy
(ΔH) for a reaction.
 If more energy is absorbed when bonds are reformed, the reaction is endothermic. If more energy is released
when bonds are broken, the reaction is exothermic.

Bond Dissociation Energy

Bond dissociation energy is the energy required to break a
given chemical bond and average bond energies are
published in tables like the one on page 351 or 307 of your
textbook. The bond dissociation energies are
experimentally determined and depend on the types of
atoms and bonds in a molecule. For this reason, average
bond energies are used to predict the enthalpy changes in
chemical reactions. Multiple bonds tend to be short and
stronger than their single bond counterparts. Since more
electrons are shared between the atoms, more energy is
required to break multiple bonds.

Be careful! When calculating the ΔH from bond energies, you need the correct structural formula to determine
the number and type of each bond and a balanced chemical equation.

Practice Problems: Use bond energies, calculate the enthalpy change for the following reactions.

1. Hydrogen gas + Chlorine gas  Hydrogen chloride gas

2. Ethyne + oxygen gas  carbon dioxide + water vapour

3. 2 C2H6O +O2  CO2 + H2O

3|Page Energy and Rates Unit

 Bond Energy Worksheet

Use bond energies to determine the energy change for the following reactions

1. Nitrogen + Hydrogen Ammonia

2. H2(g) + Cl2(g)  2HCl(g)

3. C2H4(g) + F2(g)  C2H4F2(g)

4. methane + oxygen  carbon dioxide + water

5. Hydrogen peroxide water + oxygen

H C O H
6. CΞO + 2 H-H  H

H H H H
C C H C C H

7. H-H + H H  H H

H H
H C C H
8. H H + 7 O=O  4 O=C=O + 6 H-O-H

H Cl

H C H H C Cl

9. H + 3 Cl-Cl  Cl + 3 H-Cl

H H
H C N

10. H-CΞN + H-H  H H

4|Page Energy and Rates Unit

 5.2 Calorimetry

The measurement of heat changes in chemical and physical changes

Calorimeter – a device used for making heat measurements

A calorimeter consists of:

Types of calorimeters:

1. Simple Calorimeter (constant pressure calorimeter)

2. Bomb Calorimeter (constant volume calorimeter)

Calorimetry Equations:

5|Page Energy and Rates Unit

 Calorimetry Problems

Examples:

1. To determine the enthalpy of combustion of ethyl alcohol, the following set up was used:

3.0 g of ethyl alcohol was used to heat 110.0 g of water from an

initial temperature of 24oC to a final temperature of 27.5oC.
Calculate the enthalpy of combustion of ethyl alcohol.

ethyl alcohol

2. Given the following equation: HNO3(aq) + KOH(aq) -> KNO3(aq) + H2O + 53.4 kJ
Calculate the final temperature when 55.0 mL of 1.30 M nitric acid is added to 55.0 mL of 1.30 M
potassium hydroxide. The initial temperature of both solutions was 21.4oC

3. A 100.0 g piece of erbium metal was heated to 95.0oC and dropped into 200.0 g of water, which was initially at
20.0oC. If the final temperature of the mixture was 21.5oC, calculate the specific heat capacity of erbium.

6|Page Energy and Rates Unit

 Calorimeter Activity

Purpose: To determine the enthalpy of solution of calcium chloride

Materials: solid CaCl2, balance, graduated cylinder, thermometer, calorimeter
Procedure:
1. Measure 50 mL of water and put in calorimeter
2. Obtain around 4 g of CaCl2. Record the actual mass
3. Record the initial temperature of the water
4. Add CaCl2 to the water, cover the calorimeter and stir gently
5. Measure the temperature of the solution until you see a maximum of minimum temperature. Record
this temperature.

Observations:
Solid Mass CaCl2 (g) Volume water (g) Initial Final
Temperature oC Temperature oC

CaCl2

Analysis:
1. Calculate the molar enthalpy of solution of CaCl2 in kJ/mol

2. If 75 mL of water was used instead, calculate the expected temperature change.

3. If 8.5 g of calcium chloride were used instead, calculate the expected temperature change.

4. Write the thermochemical equation for this physical change.

7|Page Energy and Rates Unit

Calorimetry and Molar Enthalpy Questions
Use the following formula to calculate the answers to the questions below. (remember that m is always for
the substance that you are measuring the temperature change, usually water or acid)
H rxn = - m(c) t
n
1) A student mixed 100.0 ml of 1.50 mol/l sulfuric acid with 200.0 ml of 1.50 mol/l sodium hydroxide. Both
solutions were at 19.67 C initially and the highest temperature reached by the reaction mixture was 34.06 C.
a) Calculate the number of moles (n) of sulfuric acid (volume in Liters times molarity in mol/l). Why not use
NaOH?

b) Calculate the total volume of the two solutions (both sulfuric acid and sodium hydroxide). This is mostly
water!

c) Calculate the mass of the two solutions combined. (m). Since it is mostly water, use the density of water 1
ml = 1 g

d) Using the information in the question, calculate the molar enthalpy of sulfuric acid.

A a) because there is one mole H2SO4 in the equation, b) 300.0mL, c) 300.0g, d) -1.20 x 102 kJ/mol H2SO4

2) Calculate the molar enthalpy for the solidification of gallium metal (Ga) if 10.0 g of gallium causes 50.0 ml
of water to change temperature from 24.0 to 27.8 C when it solidifies from a liquid. What is the
temperature change that would result if 45.0 g of Ga were used?A = -5600J/mol, t = l7 oC

3) The molar enthalpy of combustion of methane (Hrxn = -803 KJ/mol). What is the minimum mass of
methane that must be burned to warm 4.00 L of water from 22.4 to 87.6 oC, assuming no heat losses?
(Assume that 1L of water = 1Kg). A: 21.8g

4) Find the temperature increase expected for 1.00 L of water when it absorbs all the energy from the
combustion of 1.00 g of acetylene, C2H2 (g). The molar enthalpy of combustion for acetylene is 1,290
KJ/mol. Determine the amount of acetylene required to raise the temperature by 100 oC. A: t = 11.8
o
C, m=8.44g

5) In a chemistry experiment 5 g of urea NH2COHN2 is added to 150 ml of water in a simple coffee cup
calorimeter. A temperature decrease of 3.7 C is noticed. Calculate the molar enthalpy of urea. How
much urea would you use to obtain a 15 oC difference?
A : H= 34 kJ/mol , m= 20g

6) A laboratory technician initially adds 43.1 ml of concentrated 11.6 mol/L hydrochloric acid to water to
form a 500 ml solution. The temperature of the solution rises 2.6 oC.
a) Calculate the number of moles of hydrochloric acid added (molarity in mol/l times volume in liters)
b) Convert the final volume of the mixture to mass (1ml = 1g). This value is m in the formula.
c) Calculate the molar enthalpy, using the remaining information. A : H = -10 KJ/mol

8|Page Energy and Rates Unit

 Heat Transfer/ Specific Heat Problems Worksheet
Solving for Heat (Q)

1. How many joules of heat are required to raise the temperature of 550 g of water from 12.0 oC to 18.0 oC? (ans: 1.38 x
104J)

2. How much heat is lost when a 64 g piece of copper cools from 375 oC, to 26 oC? (The specific heat of copper is
0.38452 J/g xoC). Place your answer in kJ. (answer: 8.6 kJ)

3. The specific heat of iron is 0.4494 J/g x oC. How much heat is transferred when a 4.7 kg piece of iron is cooled
from 180 oC to 13 oC? Remember you must use the same units so you will have to convert your mass to grams
before you begin. (answer: -3.5 x 105J )

Solving for Mass (m)

4. 8750 J of heat are applied to a piece of aluminum, causing a 56.0 oC increase in its temperature. The specific
heat of aluminum is 0.9025 J/g x oC. What is the mass of the aluminum? (answer: 173 grams)

5. Find the mass of a sample of water if its temperature dropped 24.8 oC when it lost 870 J of heat. (answer: 8.38 g)

6. How many grams of water would require 92.048 kJ of heat to raise its temperature from 34.0 oC to 100.0 oC?
(Remember to change units first) (answer: 333 grams)

Solving for Temperature (T)

7. How many degrees would the temperature of a 450 g piece of iron increase if 7600 J of energy are applied to it?
(The specific heat of iron is 0.4494 J/g x oC) (answer: 37.6 0C)

8. A 250 g sample of water with an initial temperature of 98.8 oC loses 7500 joules of heat. What is the final
temperature of the water? (answer: 91.6 0C )

9. How much change in temperature would the addition of 35 000 Joules of heat have on a 538.0 gram sample of
copper? (Look up specific heat of copper) (answer: 169.0 0C )

Solving for Specific Heat Capacity (c)

10. Determine the specific heat of a certain metal if a 450 gram sample of it loses 34 500 Joules of heat as its
temperature drops by 97 oC. (answer: 0.79 J/g x oC )

11. 4786 Joules of heat are transferred to a 89.0 gram sample of an unknown material, with an initial temperature
of 23.0 oC. What is the specific heat of the material if the final temperature is 89.5oC? (answer: 0.809 J/g x oC )

12. The temperature of a 55 gram sample of a certain metal drops by 113 oC as it loses 3500 Joules of heat. What is
the specific heat of the metal? (answer: 0.56 J/g x oC )

9|Page Energy and Rates Unit

 Solving Bomb Calorimeter Problems

A bomb calorimeter is most often used to measure the enthalpy of combustion reactions. The
sample is placed in the inner sample cup and ignited in the presence of oxygen. The heat released
by the reaction is absorbed by two things (i) the water in the calorimeter and (ii) the calorimeter
itself. The equation used for bomb calorimeter equations is:

Note that for the calorimeter: Qcalorimeter = c ∆T where c is called the heat capacity (calorimeter constant) of the
calorimeter (heat capacity is the energy required to increase the temperature by 1oC, the mass of the calorimeter is
irrelevant)

Problems:

1. A 1.000 g sample of octane (C8H18) was burned in a bomb calorimeter containing 1200 g of water at an
initial temperature of 25.00oC. After the reaction, the final temperature of the water was 33.20oC. The
heat capacity of the calorimeter (also known as the “calorimeter constant”) is 837 J/oC. If the specific heat
of water is 4.184. J/goC, find the molar enthalpy of combustion of octane and write the thermochemical
equation.

2. A 0.500 g sample of naphthalene (C10H8) was burned in a bomb calorimeter containing 650 g of water at an
initial temperature of 20.00oC. After the reaction, the final temperature of the water was 26.4oC. If the
heat capacity of the calorimeter is 420 J/goC, determine the molar enthalpy of combustion of naphthalene.
(answer: -5140 kJ/mol)

10 | P a g e Energy and Rates Unit

3. A bomb calorimeter containing 900 g of water was calibrated by burning a sample of benzoic acid
(C6H5CO2H), whose heat of combustion is -3227 kJ/mol. When 1.890 g of benzoic acid is burned in the
calorimeter, the temperature of the water and the calorimeter increases by 8.32oC. Calculate the
calorimeter constant (heat capacity) for this calorimeter. (answer: 2243 J/goC)

4. A 1.000 g sample of the rocket fuel hydrazine (N2H4) is burned in a bomb calorimeter. The temperature
rises from 24.62oC to 28.16oC. The heat capacity of the calorimeter (including water) is 5860 J/oC.
Calculate the molar enthalpy of combustion of hydrazine. (answer: -664 kJ/mol)

5. A 0.500 g sample to TNT (C7H5N2O6) is burned in a bomb calorimeter containing 610 g of water at an initial
temperature of 20.00oC. The heat capacity of the calorimeter is 420 J/goC and the heat of combustion of
TNT is 3374 kJ/mol. Calculate the final temperature of the water and the calorimeter once the reaction is
complete. (answer: 22.5oC)

11 | P a g e Energy and Rates Unit

 Standard Molar Enthalpies of Formation

The standard enthalpy of formation, ΔH0f, for a given compound is defined

as the enthalpy change of reaction when ______________ of a compound is
formed from its constituent _____________ in their most stable state at
_________________.

The ΔH0f of any element is __________________.

Examples

1. Write a standard enthalpy of formation equation for the formation of

methane

2. Write a standard enthalpy of formation equation for the formation of

C6H12O6

Standard enthalpies of formation can be used as a "short-cut" to Hess's law if

________ is known for __________ reactants and products in a target
equation, using the following equation:

Examples:

1. Find the enthalpy of combustion of 1 mole of octane

2. Find the enthalpy of the following reaction:

Fe2O3 (s) + 3CO(g)  3CO2(g) + 2Fe(s)

3. The enthalpy of combustion of octanol is -5074.1 kJ/mol. Find ΔH0f

12 | P a g e Energy and Rates Unit

Enthalpy of Formation Questions

Data:
Some frequently used values of ∆Hf in kJ/mol are: H2O(l) = -285.8, H2O(g) = -241.8, CO2(g) = -393.5, CO(g)= -
110.5

1. The standard enthalpy of combustion of octane, C8H18, is -5512 kJ/mol. Calculate the standard enthalpy
of formation of octane, assuming that the products of its combustion are carbon dioxide and liquid
water (Answer: -201.9 kJ)

2. Ethyne, C2H2, burns in oxygen to produce carbon dioxide and liquid water. Calculate the standard
enthalpy of combustion of ethyne if its standard enthalpy of formation is +226.8 kJ/mol. (Answer: -1299.7 kJ)

3. If ethyne is burned in insufficient oxygen and the products of the reaction are carbon monoxide and
liquid water, calculate the heat released by this incomplete combustion of ethyne. (Answer: -733.7 kJ)

4. The standard enthalpy of formation of Fe2O3 is -822 kJ/mol. Calculate the enthalpy change which
accompanies the reaction between ferric oxide and carbon monoxide to produce iron and carbon
dioxide. (Answer: -27.0 kJ)

5. When sodium bicarbonate is heated, it decomposes into sodium carbonate, water vapour and carbon
dioxide. If the standard enthalpies of formation of sodium bicarbonate and sodium carbonate are -947.7
kJ/mol and -1131 kJ/mol respectively, calculate the enthalpy change of the reaction. (Answer: 129.1 kJ)

6. The standard enthalpy of combustion of cyclohexane to carbon dioxide and liquid water is -3924 kJ/mol.
What is the standard enthalpy of formation of cyclohexane? (Answer: -152.4 kJ)

7. The standard enthalpy of combustion of benzene to carbon dioxide and liquid water is -3273 kJ/mol.
What is the standard enthalpy of formation of benzene? (Answer: 54.3 kJ)

8. Calculate the enthalpy change accompanying the reaction: 2CO + 4H2  C2H5OH + H2O(g) given that
the standard enthalpy of formation of ethanol is -277.6 kJ/mol. (Answer: -298.4 kJ)

9. The standard enthalpy of formation of aqueous nitric acid is -173.2 kJ/mol and of nitrogen dioxide gas is
+33.8 kJ/mol. Calculate the enthalpy change for the following reaction:
ethanol + nitric acid  carbon dioxide gas + water vapour + nitrogen dioxide gas

(Answer: -201.6 kJ)

13 | P a g e Energy and Rates Unit

 Hess's Law

The principle of conservation of energy

Hess's law states that energy changes are_____________________. The amount

of energy depends only on the _____________ of the reactants and the state of
the products, but not on the ________________steps. Energy (enthalpy) changes
in chemical reactions are the same, regardless of whether the reactions occur in one or several steps. The total
energy change in a chemical reaction is the ______________ of the energy changes in its many steps leading to
the overall reaction.

Rules for using Hess's Law:

Hess's law can be applied to calculate enthalpies of reactions that are difficult to measure.

For example:

Find the enthalpy of combustion of ammonia: 4NH3 + 5O2  4 NO + 6H2O

GIVEN: 1. ½ N2 + ½ O2  NO ∆ H = 90.4 kJ

2. ½ N2 + 3/2 H2  NH3 ∆ H = -46.2 kJ

3. H2 + ½ O2  H2O ∆ H = -242 kJ

14 | P a g e Energy and Rates Unit

Examples:

1. Find the ∆Hcomb for C3H8O given the following:

(1) C(s) + O2(g)  CO2(g) ∆ H = -393.2 kJ

(2) ½ O2(g) + H2(g)  H2O(g) ∆ H = -241.9 kJ

(3) 3C(s) + 4H2(g) + ½O2(g)  C3H8+ ∆ H = -303.0 kJ

2. Determine the enthalpy change involved in the reaction of 300g of carbon monoxide in the following
reaction:

3H2 + CO  CH4 + H2O

Given: (1) 2H2 + O2  2H2O ∆ H = -483.6 kJ

(2) 2C + O2  2CO ∆ H = -221.0 kJ

(3) CH4 + 2O2  CO2 + 2H2O ∆ H = -802.7 kJ

(4) C + O2  CO2 ∆ H = -393.5 kJ

15 | P a g e Energy and Rates Unit

16 | P a g e Energy and Rates Unit
 6.1 Chemical Kinetics: Reaction Rates

 Thermodynamics (thermochemistry) is the study of the energy changes associated with chemical reactions;
however, it gives no information about how fast a change will take place.
 Chemical kinetics is the study of ______________________and _______________________(events at
__________________level that control the ________________and _________________of a reaction)

 Reaction rate: is expressed mathematically in terms of a _________________ in a _______________of the

_________________ or __________________ per unit time.

The rate of reaction refers to how quickly or slowly reactants are consumed, or products are formed in a reaction.

 Most commonly, reaction rate (r, mol/L•s) = change in concentration of reactant or product (ΔC, mol/L) over
time (Δt, s)

Consider the following reaction: 2 H2O2 (l) → 2 H2O (l) + O2 (g)

 The rate of loss of hydrogen peroxide, the reactant, is __________ the same as the rate of formation of
oxygen gas, the product.
 Only _________________ mole of oxygen gas is produced for every ___________ moles of hydrogen
peroxide that decomposes.
 If the average rate of H2O2 decomposition is 4.5 x 10-2 mol/L/sec, what would be the rate of:
⦿ H2O production?

⦿ O2 production?

Concentration- Time Graphs

 The shape of the curve depends on what is measured concentration of reactants OR products
 Concentration of reactant ____________over time, therefore slope will be _______________
 Concentration of product _____________ over time, therefore slope will be _______________

As the reaction proceeds, the rate _______ as the reactants

are consumed and the products are produced. Reaction rates
are usually measured at the __________ of the reaction,
where the rate of the reaction is _______________________

(i) Average Rate of Reaction:

Typically, in a reaction, the reaction rate is not constant as the reaction

progresses. The average rate of reaction gives an overall idea of how quickly
the reaction is progressing over a specific ________________________. The
average rate of reaction gives an overall idea of how quickly the reaction is
progressing over a ______________ time interval. To find the average rate:
1. Plot the concentration-time graph.
2. Draw a line between two points on the curve (___________)
3. Find the ___________ of the secant (equal to average rate)

17 | P a g e Energy and Rates Unit

Example:
If 144 g of carbon dioxide gas is produced in 1.00 minute during a chemical reaction, calculate the average rate of
reaction in terms of moles CO2 produced per second.

(ii) Instantaneous Rate of Reaction:

The instantaneous rate of reaction is the rate of reaction at a

___________________________ during the reaction. To find instantaneous
rate:
1. Plot the concentration-time graph.
2. Draw a ___________ to the curve at the specified time.
3. Find the ______________ of the tangent (equal to the
instantaneous rate)

(iii) Initial Rate of Reaction:

The speed of the reaction at the ____________ reactants are mixed

(___________)

Example:
Examine the following concentration-time curve:

a. What is the average rate of reaction from 0 to 50 seconds?

b. What is the initial rate of reaction?

Measuring Reaction Rates Experimentally

Ideally, measurements are taken without disturbing the reaction itself.

1.

2.

3.

4.

5.

6.

18 | P a g e Energy and Rates Unit

 REACTION RATES – WORKSHEET

Part 1
For the reaction data shown, calculate:

a) the average rate of reaction over the first 10 seconds.

b) the average rate of reaction over the first 60 seconds.
c) the instantaneous rate of reaction at 30 seconds.
Note on Units: M = mol/L

Part 2
1) A sample of magnesium weighing 0.360g is
dropped into dilute hydrochloric acid. At the end of 4.00 minutes, the unreacted magnesium is
removed and it is found to weigh 0.240g. Calculate the rate of the reaction in moles of magnesium reacted per
minute.

2) CH4 (g) + 2 O2 (g) → CO2(g) + 2 H2O (g)

a) 35g of CH4(g) reacts in 30.0 minutes. Calculate the rate of the reaction in moles of H4(g) reacted per hour.

b) Calculate the rate of this reaction in terms of moles of H2O(g) produced per minute.

3) If 2.3 moles of NO2 (g) are produced per minute in a reaction, how many grams of it would be produced in 2.0
hours?

4) If 5.4 moles of CO2 (g) are produced per hour in a reaction, how many hours would it take to produce 255 L of
CO2 (g) at STP?

5) 74 g of oxygen gas reacts in 15 minutes. Calculate the rate of the reaction in terms of moles of oxygen gas
reacted per hour.

6) Which of the following six reactions are likely to be a) rapid or b) slow at room temperature? Explain your
reasoning.
i) Cr2+ (aq) + Fe3+(aq)  Cr3+(aq) + Fe2+(aq)

ii) 3 Fe2+(aq) + NO3-(aq) + 4 H+ (aq)  3 Fe3+ (aq) + NO (g) + 2 H2O (g)

iii) C8H18 (g) + 12 ½ H2O(g)  8 CO2 (g) + 9 H2O (g)

iv) 2 C6H6 (g) + 7 O2 (g)  4 CO2 (g) + 6 H2O (g)

v) H+(aq) + OH- (aq)  H2O (l)

vi) Ag+ (aq) + Cl- (aq)  AgCl (s)

19 | P a g e Energy and Rates Unit

 6.2 - Rate Law and Order of Reaction

For many systems the reaction is reversible: NO2 (g) 2NO(g) + O2(g)
If the reaction rate is determined immediately after the reactants are mixed, it is assumed that the rate depends
only on the _______________________________ and the reverse reaction can be neglected. For the
decomposition of nitrogen dioxide we can write:

Rate Law Equation: An expression that shows how the rate depends on the concentration of the reactants.

Rate Constant: Proportionality constant, k, in the rate law. It is determined _____________________. The value
of the rate constant depends on how the rate is defined. The rate constant is a constant as long as the ________ is
also _____________________.
________________________: the exponent, n, used to describe the relationship between the initial concentration
of a particular reactant and the rate of the reaction It can be ____________________________. The
_________________ order of a reaction is the _____ of the individual reactant orders.
Note two important points about the above equation:
i. The concentrations of the products do not appear in the rate law because the reaction rate is being studied
under conditions where the reverse reaction does not contribute to the overall rate.
ii. The value of the exponent n must be determined by experiment; it cannot be written from the balanced
equation, unless ________________________________________________________.

Recognizing reaction order graphically:

Types of Rate Laws:

Differential Rate Law: expresses how the rate depends on ___________________. Often simply called the rate law.

Integrated Rate Law: expresses how the concentration depends on time

A given differential rate law is always related to a certain type of integrated rate law and vice versa.
The _____________ rate method is commonly used to determine the rate law equation for a reaction. This
method involves the following three steps:

i. The instantaneous rate is measured near the beginning of the reaction (before any significant changes in
reactant concentration

ii. Several different trials are performed, using ___________ initial concentrations.

iii. The results from the various trials are compared to determine the effect of ______________ on reaction
rate.

20 | P a g e Energy and Rates Unit

 Finding the Rate Law

The rate law for a reaction must be determined by experiment. The exponents, x, y, …. cannot be assumed to be
the same as the coefficients in the balanced equation.
A simple analysis of the initial rates (the instantaneous rate determined just after the reaction begins, just after
t=0) is the method of choice. In this method, the order with respect to each reactant is determined. In this method
only one reactant can be changed at a time.

Example 1: N2O5 (g)  4NO(g) + O2(g)

Experiment # [N2O5] (mol/L) Initial Rate (mol/Ls)
1 0.100 3.62 x 10-5
2 0.200 7.29 x 10-5

Example 2: 2HgCl2 + C2O4-  2Cl- + 2CO2 + Hg2Cl2

Experiment # [HgCl2] (mol/L) [C2O4-] (mol/L) Initial Rate (mol/Ls)
1 0.100 0.200 3.0 x 10-5
2 0.100 0.400 1.2 x 10-4
3 0.050 0.400 6.2 x 10-5

Example 3: BrO3- + 5Br- + 6H+  3Br2 + 3H2O

Experiment # [BrO3-] (mol/L) [Br-] (mol/L) [H+] (mol/L) Initial Rate (mol/Ls)
1 0.1 0.1 0.1 8.0 x 10-4
2 0.2 0.1 0.1 1.6 x 10-3
3 0.2 0.2 0.1 3.2 x 10-3
4 0.1 0.1 0.2 3.2 x 10-3

21 | P a g e Energy and Rates Unit

 Rates Worksheet: Initial Concentration Method

1. The following data were collected from the reaction between the hydroxide ion and t-butyl iodide, an organic halogen
compound. All the experiments were carried out at the same temperature.
(CH3)3CBr + OH-1  (CH3)3COH + Br-1
Trial Initial [(CH3)3CBr] mol / L Initial [OH1-] mol / L Initial Rate of formation of (CH3)3COH mol/L per sec.

1. 0.10 0.10 4.0 x 10-3

2. 0.20 0.10 8.0 x 10-3

3. 0.10 0.20 4.0 x 10-3

Use the data to calculate the rate law for the reaction and calculate the rate constant k.

2. The following table provides experimental data for the decomposition of acetaldehyde under certain conditions.
CH3CHO(g)  CH4(g) + CO(g) Determine the rate law for the reaction and the rate constant k.
Trial Initial [CH3CHO(g)] mol/L Initial Rate of formation of CO mol/L per sec.

1. 0.10 8.6 x 10-4

2. 0.20 3.44 x 10-3

3. The reaction between the iodide and peroxydisulfate ion in aqueous solution was studied by following the rate of
production of iodine for different initial concentrations of the reactants. 2I 1- (aq) + S2O82- (aq)  I2(aq) + 2 SO42- (aq)
Trial Initial [I1-] mol / L Initial [S2O82-] mol / L Initial Rate of formation of I2 mol/L per sec.

1. 0.04 0.04 6.25 x 10-6

2. 0.08 0.04 12.5 x 10-6

3. 0.04 0.08 12.5 x 10-6

Determine the rate law for the reaction and the rate constant k.

4. For the general reaction A + B  products the following data were obtained:
Trial Initial [A] mol / L Initial [B] mol / L Initial Rate of formation of products mol/L per sec.

1. 0.10 0.20 3.0 x 10-2

2. 0.20 0.20 6.0 x 10-2

3. 0.20 0.30 6.0 x 10-2

a) Determine the order of the reaction with respect to both A and B
b) Write the rate law for the reaction.
c) Calculate k, the rate constant.

22 | P a g e Energy and Rates Unit

5. For the general reaction A + B  products the following data were obtained :
Trial Initial [A] mol / L Initial [B] mol / L Initial Rate of formation of products mol/L per sec.

1. 0.10 0.10 4.0 x 10-2

2. 0.20 0.20 1.6 x 10-1

3. 0.20 0.10 8.0 x 10-2

a) Determine the order of the reaction with respect to both A and B b) Write the rate law for the reaction.
C) Calculate k, the rate constant.

6. For the general reaction M + N  P + Q the following data were obtained:

Trial Initial [M] mol / L Initial [N] mol / L Initial Rate of disappearance mol/L per sec.

1. 0.10 0.010 2.5 x 10-3

2. 0.20 0.010 5.0 x 10-3

3. 0.20 0.030 4.5 x 10-2

a) Determine the order of the reaction with respect to both M and N b) Write the rate law for the reaction.
c) Calculate k, the rate constant.

7. Cyclopropane, C3H6, is a gas used as a general anaesthetic. It undergoes a slow molecular rearrangement to propylene. At
a certain temperature, the following data were obtained relating concentration and rate. Determine the rate law for the
reaction and the rate constant k.
Trial Initial [C3H6] mol/L Initial Rate of formation of products mol/L per sec.

1. 0.050 2.9 x 10-5

2. 0.100 5.90 x 10-5

3. 0.150 8.85 x 10-5

8. The reaction of iodide ion with hypochlorite ion, OCl1- follows the equation : OCl1- + I1-  OI1- + Cl1-
It is a rapid reaction which gives the following rate data:
Trial Initial [OCl-] Initial [I1-] mol/L Initial Rate of formation of Cl1- mol/L per sec.

1. 1.7 x 10-3 1.7 x 10-3 1.75 x 10-4

2. 3.4 x 10-3 1.7 x 10-3 3.50 x 10-4

3. 1.7 x 10-3 3.4 x 10-3 3.50 x 10-4

Determine the rate law for the reaction and the rate constant k.

23 | P a g e Energy and Rates Unit

 6.3 Collision Theory and Rates of Reaction

For a chemical reaction to occur, the reacting particles must ______________ with each other.

Conditions for an Effective Collision

1. Particles must collide with ___________________to break the bonds in the reacting particles.

2. Particles must collide with the proper _____________geometry.

Sample Calculation:
Q: There are 1000 collisions per second in a chemical reaction. Not every collision results in a reaction. In fact, only
one reaction will occur for every 100 collisions. What is the rate of reaction?
A:

Activation Energy Ea

Transition state –

Activated complex –

Collision Energy – depends on ____________________________________________________

Maxwell-Boltzmann Distribution Curve

• A Maxwell-Boltzmann distribution curve shows the relationship between the number of
_________________ vs _______________ at a given temp.

Number of
collisions

Reaction Rate Depends on:

1. Frequency of collisions. 2 Fraction of effective collisions.

24 | P a g e Energy and Rates Unit

kinetic energy (kJ)

 Factors That Affect Reaction Rates

Factor Explanation Diagrams

Temperature
Concentration
Surface Area
Catalyst
Nature of the
Reactants

25 | P a g e Energy and Rates Unit

26 | P a g e Energy and Rates Unit
27 | P a g e Energy and Rates Unit
 6.4 Reaction Mechanisms
•Most reactions will not proceed in a single step
•The step-by-step pathway by which a reaction occurs is called the _____________________
•Each step in the mechanism is called an ______________________________________
 An elementary step consists of a _____________________________________________
 A molecular event consists of a ___________________________ in which reactants collide
______________________ with the ___________________________ and sufficient _______________

Nitrogen monoxide is a pollutant in automobile exhaust. The mechanisms whereby nitrogen monoxide reacts with
oxygen to form nitrogen dioxide (another pollutant) is believed to consist of the following elementary steps:
Step (1) NO + NO  N2O2
Step (2) N2O2 + O2  2 NO2

Leads to the overall reaction equation:

N2O2 is a reaction ________________________________: which is a species that appears in a reaction mechanism

________________ in the ________________________________________ or rate law; such species produced by
one elementary reaction must be consumed by another. They can be atoms, molecules or ions. They are very short
lived and are usually difficult, although not impossible, to isolate.

Characteristics of Elementary Reactions

•Molecularity:

Types of molecularity:
1. Unimolecular-
2. Bimolecular –
3. Termolecular reactions (simultaneous collision of three molecules) are rare because:

Rate Laws and Elementary Steps

A rate law equation can be written for an elementary step. The __________________ for each reactant in an
elementary step is the ___________the ___________________________. This is not true for the overall rate law
and the overall balanced equation.

Rate Determining Step:

Every mechanism has a rate-determining step. This is the ______________________ in the reaction. If the first
elementary step of the mechanism is the rate-determining step, then we can say that the overall reaction rate
depends on this initial step and on the concentrations of the species involved in this step.
Any subsequent step is faster and does not affect the overall rate.

Kinetic experiments of the reaction of nitrogen dioxide with carbon monoxide show that the rate of this reaction
depends on the concentration of the nitrogen dioxide to the power of two. Further
experimental evidence indicates the existence of nitrogen trioxide as a reaction
intermediate. A proposed mechanism for this reaction would then be the following:

step 1 NO2 + NO2  NO3 + NO slow rate =

step 2 NO3 + CO  NO2 + CO2 fast rate =
Since two molecules of nitrogen dioxide are involved in the rate determining step, the
rate law is Rate =

What is the equation for the overall reaction?

What is the intermediate?

28 | P a g e Energy and Rates Unit
What is the rate law for the reaction?

Reaction mechanisms are only educated guesses at the behaviour of molecules, but there are three rules that must
be followed in proposing a mechanism:
1. 2. 3.

Catalysts
A catalyst lowers the activation energy of a reaction by providing an __________________ mechanism. The rate of
the reverse reaction is also ___________________.

Problems:

29 | P a g e Energy and Rates Unit

 Worksheet - Reaction Mechanisms
c) What is an intermediate in this mechanism?
1. It is known that compounds called chlorofluorocarbons (C.F.C.s) (eg.
CFCl3) will break up in the presence of ultraviolet radiation, such as d) Given that the uncatalyzed overall reaction is a slow exothermic
found in the upper atmosphere, forming single chlorine atoms: reaction, draw a potential energy graph which shows the possible
CFCl3  CFCl2 + Cl shape of the curve for the uncatalyzed reaction. On the same graph,
show a possible curve for the catalyzed reaction.
The Cl atoms then react with Ozone (O3) as outlined in the following
mechanism.

Step 1: Cl + O3  ClO + O2

Step 2: ClO + O  Cl + O2 (single "O" atoms occur

naturally in the atmosphere.)

a) Write the equation for the overall reaction. (Using steps 1 and 2) Progress of Reaction
3. Consider the following mechanism:

b) What is the catalyst in this reaction?

Step 1: H2O2 + I-  H2O + IO- (slow)
c) Identify an intermediate in this reaction
Step 2: H2O2 + IO-  H2O + O2 + I- (fast)
d) Explain how a small amount of chlorofluorocarbons can destroy a
large amount of ozone. a) Give the equation for the overall reaction.

b) What acts as a catalyst in this mechanism?

e) What breaks the bond in the CFCl3 and releases the free Cl atom? c) What acts as an intermediate in this mechanism?

4. What is meant by the rate determining step in a reaction mechanism?

2. Given the following mechanism, answer the questions below:

Step 1: O3 + NO  NO2 + O2 (slow)

5. What is meant by a reaction mechanism?
Step 2: NO2 + O  NO + O2 (fast)

a) Give the equation for the overall reaction.

6. How are reaction mechanisms determined?
b) What could the catalyst be in this mechanism?
30 | P a g e Energy and Rates Unit
7. Given the following Potential Energy Diagram for a 3-step reaction, h) In a dashed line or another colour sketch a possible curve that
answer the questions below it: would represent the route for the uncatalyzed overall reaction. Label
this on the graph.

8. Given the reaction: 4HBr + O2  2H2O + 2Br2

a) Would you expect this reaction to take place in a single step? Why
or why not?

b) This reaction is thought to take place by means of the following

mechanism:

Step 1: HBr + O2  HOOBr (slow)

Step 2: HBr + HOOBr  2HOBr (fast)

a) Which arrow indicates the activation energy for the first step of Step 3: 2HBr + 2HOBr  2H2O + 2Br2 (fast)
the reverse reaction?
c) Identify the two intermediates
b) Which arrow indicates the activation energy for the first step of
d) A catalyst is discovered which increases the rate of Step 3. How will
the forward reaction?
this affect the rate of the overall reaction? Explain your answer.
c) Which arrow indicates the activation energy for the second step of
the forward reaction?
e) A catalyst is discovered which increases the rate of Step 1. How
will this affect the rate of the overall reaction? Explain your answer.
d) Which arrow indicates the enthalpy change (∆H) or "enthalpy
change" for the overall forward reaction?

e) Which arrow indicates the enthalpy change (∆H) or "enthalpy

f) Which step has the greatest activation energy?
change" for the overall reverse reaction?
g) How many "bumps" will the potential energy diagram for the
f) Which arrow indicates the activation energy for the overall reaction mechanism have?
forward reaction? h) Which step is called the rate determining step in this mechanism?

g) Which step would be the rate determining step in the forward i) In order to have successful collisions, the colliding particles must
reaction? have both the proper amount of energy and the proper ___________

31 | P a g e Energy and Rates Unit

 j) On the set of axes below, draw the shape of the curve you might Potential
Energy
expect for the reaction. The overall reaction is exothermic The overall reaction is.
Potential
Energy

Progress of Reaction Progress of Reaction

9. The equation for an overall reaction is: I- + OCl-  IO- + Cl-
10. Given the following steps for a mechanism:
a) The following is a proposed mechanism for this reaction. One of
the species has been left out. Determine what that species is and Step 1: Br2  2Br (fast)
write it in the box. Make sure the charge is correct if it has one!
Step 2: Br + OCl2  BrOCl + Cl (slow)
Step 1: OCl- + H2O  HOCl + OH- ( fast )
Step 3: Br + Cl  BrCl (fast)
Step 2: I- + HOCl  IOH + Cl- ( slow )
a) Write the equation for the overall reaction.
Step 3: IOH + OH-  + H2O ( fast )

b) Which species in the mechanism above acts as a catalyst? b) A substance is added that decreases the activation energy for step
c) Which three species in the mechanism above are intermediates? Will this speed up, slow down, or have no effect on the
d) Step ______________ is the rate determining step. rate of the overall reaction? Give a reason for your answer.

e) On the set of axes below, draw the shape of the curve you might
expect for the reaction in this question. The overall reaction is
endothermic! Make sure you get the "bumps" the correct relative c) Is there a catalyst in this mechanism? __________. If so, what is
sizes. it? ____________

d) Is there an intermediate in this mechanism?________. If so, what

is it? __________

e) Which step is the rate determining step?

32 | P a g e Energy and Rates Unit

 12. A certain chemical can provide a reaction with an alternate
11. The following potential energy diagram refers to a very slow one- mechanism having a greater activation energy. What will happen to
step reaction of ozone (O3) and oxygen atoms in the upper the rate of the reaction when this chemical is added? Explain.
atmosphere.

13. The following overall reaction is fast at room temperature:

H+ + I- + H2O2  H2O + HOI

A student proposes the following two-step mechanism for the above
reaction:

Step 1 : H+ + H+ + H2O2  H4O22+

Step 2 : H4O22+ + I -  H2O + HOI + H+

Would you agree or disagree with this proposed mechanism? Why?

On the axis below, draw a potential energy diagram which could
represent the catalyzed mechanism for the reaction:
14. Consider the following reaction: CO + NO2  CO2 + NO
Step 1: O3 + NO  NO2 + O2 (slow) a) The first step in each of two proposed reaction mechanisms for the
above reaction is listed below. If each proposed reaction
Step 2: NO2 + O  NO + O2 (fast) mechanism
consists of only two steps, determine the second step for each mecha
250
Proposed Mechanism One:

200 Step 1: 2NO2  NO3 + NO (slow)

Step 2: __________________________________________ (fast)
150
Proposed Mechanism Two:
PE (kJ)

100 Step 1: 2NO2  N2O4 (fast)

Step 2: __________________________________________ (slow)
50
b) Experimental data show that the rate of the reaction is not
affected by a change in the [CO]. Which of these two mechanisms
0
0
would be consistent with these data? Explain your answer.
Progress of Rea ction
33 | P a g e Energy and Rates Unit
 Rates Review Sheet c) If pentane is consumed at an average rate of 0.030 moles/s, determine
the rate of consumption of oxygen in moles/s.
1. A chemist wishes to determine the rate of reaction of beryllium with
hydrochloric acid. The equation for the reaction is: _______
Be(s) + 2HCl(aq)  H2(g) + BeCl2(aq) d) If pentane is consumed at an average rate of 0.030 moles/s, determine
A piece of beryllium is dropped into 1.00 L of HCl(aq) and the the rate of production of CO2 in moles/s.
following data were obtained:

Time (s) Mass of Beryllium (g) _

e) If pentane is consumed at an average rate of 0.030 moles/s,

determine the rate of production of CO2 in grams/s.

a) Calculate the Rate of Reaction in grams of Be consumed per second.

3. On the following set of axes, draw the shape of the curve you would
b) Calculate the Rate of Reaction in moles of Be consumed per second. expect if you plotted the [HCl] vs. Time, starting immediately after
A______________
the two reactants are mixed. The equation for the reaction is:
Zn(s) + 2HCl(aq)  H2(g) + ZnCl2(aq)
c) What will happen to the [HCl] as the reaction proceeds?

2. When pentane (C5H12) is burned in air (oxygen), the products carbon

[HCl]

dioxide and water are formed.

a) Write a balanced formula equation for this reaction.

b) If pentane is consumed at an average rate of 2.16 grams/s, determine

the rate of consumption of pentane in moles/s.
Time
_________________
Explain how you got that particular shape. Be detailed.

34 | P a g e Energy and Rates Unit

4. How many possible collisions are there between 3 H2 molecules and Approximately what fraction of the molecules in the sample have enough
3 I2 molecules? (a diagram may help) energy for an effective collision?
_______________

b) On the diagram in question "a", draw the curve you would expect at
a higher temperature in which the rate of the reaction is doubled. Be
5. a) In a room filled with H2 and O2 there are about 1032 collisions per
careful to be accurate! Label it.
second. Explain why the reaction between H2 and O2 at room
temperature is so slow as to be unnoticeable! 8. a) When two moles of A react with one mole of B, a reaction occurs
in which three moles of C are formed and 34.5 kJ of heat are given
off. Write an equation for this reaction showing the heat of reaction
(∆H) at the right of the equation.

b) Suggest two ways in which the reaction in question "5a" could be

speeded up.
b) Write a thermochemical equation for the reaction in (a) (ie. the Heat
Term is right in the equation.)

6. What might be done to a solid catalyst to make it more efficient?

c) Write a thermochemical equation which shows what happens when

7. a) The following diagram shows a graph of Number of Particles vs. the 3 moles of C decompose to form two moles of A and 1 mole of B. (See
Kinetic Energy for a sample of molecules colliding: the reaction in "b")

d) What would happen to the temperature of the surroundings if the

reaction mentioned in "a" was carried out? _______ This type of
reaction which releases heat is called__________________________

e) In the reaction mentioned in question "a" which has more enthalpy,

the reactants or the products?

f) What is meant by enthalpy?

35 | P a g e Energy and Rates Unit

9. Use the following Potential Energy Diagram to answer all the
questions below: j) What happens to the kinetic energy (speed) of AB and A as the
reaction on as shown on the graph proceeds past the activated
complex and toward the products?

k) For A2 and B to form the activated complex they must have the proper
energy and the proper__________________________________

l) If a catalyst C is used in this reaction, it takes place by means of a

different mechanism. This one involves two steps.

A2 + C  AC + A (slow)

AC + B  AB + C (fast)

Draw another curve on the graph with another colour showing the
a) What is the value of ∆H for the forward reaction ? catalyzed reaction. (Remember it has two steps so it should have two
bumps! Also be aware that one of the bumps is higher than the other!
b) What is the value of the activation energy for the forward reaction?

m) Which step in question (l) is the rate determining step?

c) What is the value of the activation energy for the reverse reaction?
n) Looking at only the equations for the steps in question "l", how could
one tell that "C" is a catalyst?
d) Which is a stronger bond, A--A or A--B ?

e) Explain your answer to (d) o) What is ∆H for the reverse reaction to what is shown on the graph?

p) What effect did the catalyst have on the activation energy for the
f) Which species is the activated complex? forward reaction? For the reverse reaction?

g) Which set of species has the lowest potential energy?

h) Is the reaction as written endothermic or exothermic? q) What effect did the catalyst have on the ∆H of the forward reaction? ______
The reverse reaction?
i) What is the minimum energy needed to start the reaction
AB + A  A2 + B ?

36 | P a g e Energy and Rates Unit

10. Name four instances in which catalysts are used in industry or c) C3H8 (g) + 5O2 (g)  3CO2 (g) + 4H2O (g)
everyday life and tell which catalysts are used.
d) Fe (s) + S(s)  FeS (s)

15. State whether the following are endothermic or exothermic .

a) S + O2  SO2 ∆H = -297 kJ
11. Describe what happens to the kinetic energy, potential energy and
the total energy of reactant molecules as they approach each other.
b) NO2 - 33.8 kJ  1/2 N2 + O2

c) N2 + O2 + 90.4 kJ  2NO

12. Explain why a lower activation energy for a reaction leads to a d) N2H4 + O2  N2 + H2O + 627.6 kJ
greater reaction rate at a given temperature.
16. Consider the reaction:

Ca(s) + 2HBr (aq)  H2 (g) + CaBr2 (aq) + heat

13. A small piece of zinc react with 2.0 M HCl to produce 12.0 mL of H2
gas in 30.0 seconds. Calculate the rate of reaction State whether the following changes would increase the rate:

a) In mL of H2/second a) Let the CaBr2 solution evaporate without changing the temperature.

b) Allow the H2 (g) to escape

c) Decrease the temperature.

b) In moles of H2/second
d) Increase the temperature.

e) Increase the [HBr]

14. Which of the following reactions is most likely to have the greatest
rate at room temperature? 17. Consider the rate of the following reaction:

a) Ag+(aq) + I- (aq)  AgI(s) Sn(s) + 2HCl(aq)  H2(g) + SnCl2(aq)

b) H2 (g) + Cl2 (g)  2HCl (g) a) Is it dependent on temperature? Explain your answer.

37 | P a g e Energy and Rates Unit

b) Is it dependent on pressure? Explain your answer.

c) Is it dependent on surface area? Explain your answer.

18. Consider the following reaction:

2NO(g) + 2H2(g)  N2(g) + 2H2O(g)

Data collected for the above reaction was used to construct the
following graph:

0.04

Moles NO

0.03

0.02 a) Determine the Activation Energy for the forward reaction

0.01
b) Determine the Activation Energy for the reverse reaction

c) What is the Enthalpy Change (∆H) for the forward reaction?

0.00
0 1 2 3 4 5 6 7 8 9 10
d) What is the Enthalpy Change (∆H) for the reverse reaction?
Tim e (s)

From this graph, determine the rate of reaction in moles of NO e) The forward reaction is _____________thermic.
consumed per second.
f) The reverse reaction is ______________thermic.

g) Which species or set of species forms the Activated Complex?

19. Use the following Potential Energy Diagram to answer the questions h) Which bond is stronger, A--B or B--C?___________________. Give a
below: reason for your answer.

i) Particles from which species or set of species is moving the fastest? ___________

38 | P a g e Energy and Rates Unit

j) Particles from which species or set of species is moving most slowly? ___________
c) Which arrow indicates the activation energy for the second step of the
forward reaction? ____
k) The compound "AB" is a gas and the element "C" is a solid. What effect
would grinding "C" into a fine powder have on the graph shown here? d) Which arrow indicates the enthalpy change ( H) or "heat of reaction"
for the overall forward reaction? ____

e) Which arrow indicates the enthalpy change ( H) or "heat of reaction"

20. What two requirements must be met before a collision between two for the overall reverse reaction? ____
reactant particles is effective?
f) Which arrow indicates the activation energy for the overall forward
reaction?

g) Which step would be the rate determining step in the forward

21. Describe what happens to two reactant particles which collide with reaction? _____
less energy than the Activation Energy.

23. Given the reaction: HCOOH  CO + H2O

22. Given the following Potential Energy Diagram for a 3 step reaction,
answer the questions below a) This reaction, without a catalyst, is very slow at room temperature.
Suggest why. __

b) This reaction is thought to take place by means of the following

mechanism when the catalyst H+ is added:

Step 1: HCOOH + H+  HCOOH2+ (fast)

Step 2: HCOOH2+  H2O + HCO+ (slow)

Step 3: HCO+  CO + H+ (fast)

c) Identify the two intermediates

a) Which arrow indicates the activation energy for the first step of the d) Identify the catalyst in this mechanism
reverse reaction? _______
e) Another catalyst is discovered which increases the rate of only Step 1.
b) Which arrow indicates the activation energy for the first step of the How will this affect the rate of the overall reaction? Explain.
forward reaction?
39 | P a g e Energy and Rates Unit
f) Which step has the greatest activation energy? a) The following is a proposed mechanism for this reaction. One of the
species has been left out. Determine what that species is and write it
g) How many "bumps" will the potential energy diagram for the catalyzed in the box. Make sure the charge is correct if it has one!
reaction have?
Step 1: OCl- + H2O  HOCl + OH- ( fast )
h) Which step is called the rate determining step in this mechanism? _______________

i) In order to have successful collisions, the colliding particles must have Step 2: I- +  IOH + Cl- ( slow )
both the proper amount of energy and the proper __________________________________________
Step 3: IOH + OH-  IO - + H2O ( fast )
f) On the set of axes below, draw the shape of the curve you might expect
for the reaction in this question. The overall reaction is exothermic! b) Which species in the mechanism above acts as a catalyst?

c) Which three species in the mechanism above are intermediates?

d) Step ______________ is the rate determining step.

24. Given the following mechanism, answer the questions below:

Step 1: O3 + NO  NO2 + O2 (slow)
Step 2: NO2 + O  NO + O2 (fast)
a) Give the equation for the overall reaction. e) On the set of axes below, draw the shape of the curve you might expect
for the reaction in this question. The overall reaction is endothermic!
Make sure you get the "bumps" the correct relative size
b) What could the catalyst be in this mechanism?
c) What is an intermediate in this mechanism?

25. The equation for an overall reaction is: I- + OCl-  IO- + Cl-

40 | P a g e Energy and Rates Unit