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A gas adapts the shape of the container and fills the container since its particles are far and
move randomly
A liquid adopts the shape of the container to the extent of the container’s volume since its
particles are close together but free to move around each other
A solid has a fixed shape regardless of the shape of the container, because its particles are
close together and held rigidly in place
Several other aspects distinguish gases from liquids and solids
o The volume of a gas changes significantly with pressure
Increasing the force decreases the volume
Gases under pressure can do a lot of work
Eg. Rapidly expanding air in jackhammer breaks rock and cement
o The volume of gas changes significantly with temperature
Expands when heated and shrinks when cooled
Volume change is 50 to 100 times greater than for solids and liquids
Eg. Lifting a rocket into space
o Gases flow very freely
Allows gases to be transported more easily through pipes
Can also leak out more rapidly
o Gases have relatively low densities
The density of gas is measured in g/L, whereas the density of liquids is usually
g/mL, which is 1000 times as dense
Density increases when a gas cools since its volume decreases
o A gas forms a solution of any proportion
Eg. Air is a solution of 18 gases
These properties of gas arrive because the particles are much further apart than those in either
a liquid or solid
Four independent variables describe the physical behaviour of a gas: pressure (𝑝), volume
(𝑉), temperature (𝑇), and amount (𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑚𝑜𝑙𝑒𝑠, 𝑛)
o The variables are interdependent: any one can be determined by measuring the other 3
Three key relationships among the four gas variables: Boyle’s Law, Charles’s Law and
Avogadro’s Law
o Each of these laws expresses the effect of one variable on another, with the remaining
two variables held constant
o The individual gas laws are special gases of the ideal gas law, which describes the
behaviour of an ideal gas
Ideal Gas: A gas that exhibits linear relationships among volume, pressure, temperature and
amount
o No ideal gas exists, but most simple gases and noble gases behave nearly ideal at
ordinary temperatures and pressures
Boyle’s Law- The relationship between volume and pressure
One mole of any ideal gas occupies the same volume at a given temperature and pressure,
hence, differences in density depend on the difference in molar mass
o Eg. At STP 1 mol of O2 occupies the same volume as 1 mol N2, however, O2 is denser
since each O2 molecule has a greater mass than each N2 molecule
Rearrange the ideal gas law to calculate the density of gas from its molar mass
𝑚 𝑚
𝑛= ,𝑑=
Μ V
ΜP
𝑑 = 𝑅𝑇
o Two important ideas are expressed by this equation:
The density of gas is proportional to its molar mass
Volume remains constant, but a gas with a greater mass has greater density
The density of a gas is inversely proportional to the temperature
As the volume of a gas increases with temperature, the same mass occupies
a greater space, so the density decreases
Molar mass of the gas and the ideal gas law
𝑚 𝑝𝑉
𝑛= =
Μ 𝑅𝑇
mRT
Μ=
𝑝𝑉
Gases mix homogenously (from a solution) in any proportion
Each gas in the mixture behaves as if it were the only gas present (assuming no chemical
interactions)
Dalton’s Laws of Partial Presures
o Observed the total air pressure increase by the pressure of water vapour when added
o In a mixture of unreacting gases, the total pressure is the sum of the partial pressures of
the individual gases:
𝑝𝑡𝑜𝑡𝑎𝑙 = 𝑝1 + 𝑝2 + ⋯
𝑛 𝑅𝑇 𝑛 𝑅𝑇
𝑃1 = 1𝑉 and 𝑃2 = 2𝑉
𝑛 𝑅𝑇 𝑛 𝑅𝑇 (𝑛 +𝑛 )𝑅𝑇 𝑛 𝑅𝑇
𝑝𝑡𝑜𝑡𝑎𝑙 = 𝑝1 + 𝑝2 = 1𝑉 + 2𝑉 = 1 𝑉2 = 𝑡𝑜𝑡𝑎𝑙𝑉
o Each component in the mixture contributes a fraction to the total number of moles in
the mixture, known as the mole fraction
𝑛1 𝑛
𝑋1 = = 1
𝑛𝑡𝑜𝑡𝑎𝑙 𝑛1 +𝑛2
o The partial pressure of a gas is the total pressure multiplied by the mole fraction
𝑝1 = 𝑋1 ∙ 𝑝𝑡𝑜𝑡𝑎𝑙
When a gas is in contact with water, some of the water vapourizes into the gas
o The total pressure is the sum of the gas pressure and the vapour pressure of water at the
given temperature
Kinetic-Molecular Theory is a model that accounts for macroscopic gas behaviour at the
level of individual particles
o Postulate 1: Partial Volume
A gas consists of a collection of individual particles and empty space between
them
The volume of each particle is so small compared to the volume of the sample
that it is assumed to be zero
Concept of ideality relies on the necessity that particles move about
independently without exerting forces upon another
o Postulate 2: Particle Motion
The particles are in constant, random, straight-line motion, except when they
collide with the container walls or with eachother
o Postulate 3: Particle Collisions
The collisions are elastic: the colliding molecules exchange energy but do not
lose any energy through friction
Their total kinetic energy is constant
Between collisions, the molecules do not influence each other by attraction or
repulsive forces
Each particle has a molecular speed (u)
Most particles are moving near the most probable speed, but some are faster while others are
slower
o The most probable speed increases as the temperature increases
o The average kinetic energy of the molecules is proportional to the absolute temperature
o ̅̅̅̅
𝐸𝐾 ∝ 𝑇 or ̅̅̅𝐸𝐾̅ = 𝑐 ∙ 𝑇
o Where ̅̅̅ 𝐸𝐾̅ is the average kinetic energy of the molecules and 𝑐 is a constant that is the
same for any gas
At any given temperature, all gases have the same kinetic energy
Origin of pressure
o Each gas particle colliding with the container walls exerts a force
o Countless collisions over the inner surface results in a pressure
Boyle’s Law
o Before any change in pressure, the pressure exerted by the gas equals the pressure
exerted on the gas
o As external pressure increases, the average distance between the molecule and the wall
decreases, so the volume decreases
o Collisions become more frequent over a shorter average distance, which gases the gas
pressure to increase until it equals the external pressure
Dalton’s Law of Partial Pressures
o Adding a given amount of gas will increase the number of particles, which increases
the collision rates and therefore the pressure
o Each gas exerts a fraction of the total pressure
Charles’s Law
o At some starting temperature, the external pressure equals the gas pressure equals the
external gas pressure
o When the gas is heated and the temperature increases
The most probable molecular speed and average kinetic energy increase, causing
the particles to hit the mole more frequently and more energetically
As a result, the volume increases until the two pressures are equivalent
Avogadro’s Law
o When gas is added, the particles hit the walls more frequently, which temporarily
increases pressure
o As a result, the volume increases until the two pressures are equivalent
1
𝐸𝑘 = 𝑚𝑣 2
2
o A heavier object moving slower can have the same kinetic energy as a lighter object
moving faster
o The most probable speed increases as the molar mass decreases
The Kinetic-Molecular theory has two postulates that do not reflect the following
o Gas particles are not points of mass, but have volumes determined by the sizes of their
atoms and the length and direction of their bonds
o Attractive and repulsive forces exist among gas particles because atoms contained
charged subatomic particles and many bonds are polar
o These real situations cause deviations from ideal behaviour under extreme conditions
of lower temperature and high pressure
Effects of extreme conditions on gas behaviour
o Even at STP, gases deviate slightly from ideal behaviour
Deviations increase as boiling point rises
o Phenomena that cause deviations exert more influence as temperature decreases and
pressure increases
𝑝𝑉
o At high 𝑃𝑒𝑥𝑡 , values are lower than ideal values because of interparticle attractions
𝑅𝑇
Interparticle attractions caused by imbalances in electron distributions occur
𝑝𝑉
between separate molecules, which lowers the pressure and decreases 𝑅𝑇
At normal 𝑃𝑒𝑥𝑡 , the distances are so great that attractions are negligible
As 𝑃𝑒𝑥𝑡 rises, the volume of the sample decreases and the particles get closer, so
interparticle attractions have a greater effect
Attraction to nearby particles causes the impact against the container wall to
lessen
This effect results in decreases gas pressure
Similarly, lowering the temperature slows the particles, so they attract each other
for a longer time
𝑝𝑉
o At lower 𝑃𝑒𝑥𝑡 , values are greater than ideal values because of particle volume
𝑅𝑇
At normal 𝑃𝑒𝑥𝑡 , the space between the particles (free volume) is enormous
compared to the volume of the particles themselves (particle volume)
Thus, free volume was essentially equivalent to V, the container volume
At moderately high 𝑃𝑒𝑥𝑡 , the particle volume takes up an increasing proportion of
the container volume
At extremely high 𝑃𝑒𝑥𝑡 , the large particle volume makes the free volume
significantly less
o Work (𝑤): All other forms of energy transfer involve some type of work, the energy
that is transferred when an object is moved by a force
Eg. When you (system) kick a football, energy is transferred as work because the
force of the kick moves the ball and the air (surroundings)
The total change in a system’s internal energy is the sum of the energy transferred as heat
and/or work
o ∆𝑈 = 𝑞 + 𝑤
The values of 𝑞 and 𝑤 (and therefore the value of ∆𝑈) can have either a positive
or negative sign
We define the sign purely out of the system’s perspective:
Energy transferred into the system is positive, because the system ends up with
more energy
Energy transferred out of the system is negative, because the system ends up with
less energy
o For a system that only transfers heat (𝑞) and no work (𝑤): 𝑤 = 0, ∆𝑈 = 𝑞
Heat flowing out of the system: The final energy of the system is less than the
initial, so heat was released, making 𝑞 negative and therefore ∆𝑈 is negative
Heat flowing into the system: The final energy of the system is higher than the
initial, so heat was absorbed, making 𝑞 is positive and therefore ∆𝑈 is positive
o For a system that only transfers work (𝑤) and no heat (𝑞): 𝑘 = 0, ∆𝑈 = 𝑤
Work done by the system: The system releases energy as work, so the final
energy of the system is less than the initial and 𝑤 is negative, therefore ∆𝑈 is
negative
Work done on the system: The system gains energy as work, so the final energy
of the system is greater than the initial and 𝑤 is positive, therefore ∆𝑈 is positive
Energy changes form but does not simply appear or disappear—energy cannot be created or
destroyed
Energy is conserved: it can change from one form to another and move into or out of a
system, but the total energy in the universe remains constant
Law of Conservation of Energy (First Law of Thermodynamics): the total energy of the
universe is constant
o ∆universe 𝑈 = ∆system 𝑈 + ∆surroundings 𝑈 = 0
Joule (𝐽): SI units of energy composed of three base units: 1 𝐽 = 1 𝑘𝑔 ∙ 𝑚2 /𝑠 2
o Both heat and work are expressed in joules
Calorie (𝑐𝑎𝑙): older unit defined originally as the quantity of energy needed to raise the
temperature of 1 g of water by 1oC
o The calorie is now expressed in terms of joules: 1 𝑐𝑎𝑙 = 4.184 𝐽
State Function: A property that is dependent only on the current state of the system (its
composition, volume, pressure and temperature), not the path that the system takes to reach
this state
o The energy change of a system can occur by countless combinations of heat (𝑞) and
work (𝑤)
o Internal Energy (𝑈) is a state function: ∆𝑈 does not depend on how the changes take
place, but only the difference between the final and initial states
o Heat (𝑞) and work (𝑤) are not state functions because their values depend on the path
that the system takes
o Pressure (𝑝), volume (𝑉) and temperature (𝑇) are some other state functions
o Path independence means that changes in state functions depend only on the initial and
final states
To find the energy change during a process, we measure the quantity of heat released or
absorbed by relating it to the change in temperature
The quantity of heat (𝑞) absorbed or released by an object is proportional to its temperature
change:
𝑞
o 𝑞 ∝ ∆𝑇 or 𝑞 = constant(∆𝑇) or = constant
∆𝑇
Heat Capacity: the quantity of heat required to change the temperature of an object by 1 K,
which is dependent on the object itself and varies between objects
𝑞 𝐽
o Heat Capacity = (𝑖𝑛 )
∆𝑇 𝐾
Specific Heat Capacity (𝑐): the quantity of heat required to change the temperature of 1 g of
a substance by 1 K
𝑞 𝐽
o Specific Heat Capacity (𝑐) = (𝑖𝑛 )
(𝑚𝑎𝑠𝑠)(∆𝑇) 𝑔∙𝐾
o If we know the 𝑐 of the object being heated or cooled, we can measure the mass and
temperature change, and calucalte the heat absorbed or released:
o 𝑞 = (𝑐)(𝑚𝑎𝑠𝑠)(∆𝑇)
When an object gets hotter (∆𝑇 > 0), 𝑞 > 0
When an object gets cooler (∆𝑇 < 0), 𝑞 < 0
Metals have relatively low 𝑐, while water has a high value
Molar Heat Capacity (𝐶𝑚 ): the quantity of heat required to change the temperature of 1 mol
of a substance by 1 K
𝑞 𝐽
o Molar Heat Capacity (𝐶𝑚 ) = (𝑖𝑛 )
(𝑎𝑚𝑜𝑢𝑛𝑡 (𝑚𝑜𝑙))(∆𝑇) 𝑚𝑜𝑙∙𝐾
o To find 𝐶𝑚 , we multiple 𝑐 by the molar mass
Calorimeter: A device used to measure the heat released (or absorbed) by a physical or
chemical process
o Constant Pressure Calorimetry: Coffee-Cup Calorimeter
Can be used to find the specific heat capacity of a solid, as long as he solid does
not react with or dissolve in water
The solid is weighed, heated to some known temperature and added to a know
mass and temperature of water in the calorimeter
After stirring, the final water temperature is measured, which is also the final
temperature of the solid
Assuming no heat escapes the calorimeter, the heat released by the system is
equal in magnitude but opposite in sign to the heat absorbed by the surroundings
−𝑞𝑠𝑜𝑙𝑖𝑑 = 𝑞𝑤𝑎𝑡𝑒𝑟
𝑞 = (−𝑐𝑠𝑜𝑙𝑖𝑑 )(𝑚𝑎𝑠𝑠𝑠𝑜𝑙𝑖𝑑 )(∆𝑇𝑠𝑜𝑙𝑖𝑑 ) = (𝑐𝑤𝑎𝑡𝑒𝑟 )(𝑚𝑎𝑠𝑠𝑤𝑎𝑡𝑒𝑟 )(∆𝑇𝑤𝑎𝑡𝑒𝑟 )
(𝑐 )(𝑚𝑎𝑠𝑠𝑤𝑎𝑡𝑒𝑟 )(∆𝑇𝑤𝑎𝑡𝑒𝑟 )
𝑐𝑠𝑜𝑙𝑖𝑑 = 𝑤𝑎𝑡𝑒𝑟
(𝑚𝑎𝑠𝑠 )(∆𝑇 )
𝑠𝑜𝑙𝑖𝑑 𝑠𝑜𝑙𝑖𝑑
o Constant Volume Calorimetry: Bomb Calorimeter
A device commonly used to measure the heat of combustion reactions, which as
those for fuels and food
A thermochemical equation is a balanced equation that include the enthalpy change of the
reaction (∆𝐻) and the magnitude is specific for the given equation
Keep in mind that a given ∆𝐻 refers only to the amounts (mols) of substances and their states
of matter in the equation
The enthalpy change of any process has two aspects:
Sign: the sign of depends on whether or not the reaction is exothermic (-) or endothermic (+)
o A forward reaction has the opposite sign to the reverse reaction
o Decomposition of 2 mol of water to its elements (endothermic)
𝑘𝐽
𝐻2 𝑂(𝑙) = 𝐻2 (𝑔) + 𝑂2 (𝑔) ∆𝐻 = 572
𝑚𝑜𝑙
o Formation of 2 mol of water from its elements (exothermic)
𝑘𝐽
2𝐻2 (𝑔) + 𝑂2 (𝑔) = 2𝐻2 𝑂(𝑙) ∆𝐻 = −572 𝑚𝑜𝑙
Magnitude: the magnitude of ∆𝐻 is proportional to the amount of substance
o Formation of 1 mol of water from its elements (half the proceeding amount)
1 𝑘𝐽
𝐻2 (𝑔) + 2 𝑂2 (𝑔) = 𝐻2 𝑂(𝑙) ∆𝐻 = −286 𝑚𝑜𝑙
For this reaction, the formation of 1 mol of liquid 𝐻2 𝑂 releases 286 kJ of energy
Key points about thermochemical equations:
Balancing Coefficients: use fractional coefficients to balance an equation
o Specifying the magnitude of ∆𝐻 for a particular reaction for the reaction of 1/8 mol of
𝑆2 , the reaction of 1 mol of 𝑂2 or the formation of 1 mol of 𝑆𝑂2
1 𝑘𝐽
o 8 𝑆2 (𝑠) + 𝑂2 (𝑔) = 𝑆𝑂2 (𝑔) ∆𝐻 = −296.8 𝑚𝑜𝑙
Thermochemical Equivalence: for a particular reaction, a certain amount of substance is
thermochemically equivalent to a certain quantity of energy
o 298.6 kJ is thermochemically equivalent to 1/8 mol of 𝑆2 , 1 mol of 𝑂2 or mol of 𝑆𝑂2
The state-function property of enthalpy allows us to find ∆𝐻 of any reaction for which we
can write an equation
Hess’s Law: the enthalpy change of an overall process is the sum of the enthalpy change of
its individual steps:
o ∆𝑜𝑣𝑒𝑟𝑎𝑙𝑙 𝐻 = ∆1 𝐻 + ∆2 𝐻 + ⋯ + ∆𝑛 𝐻
o ∆ 𝑟 𝐻 = ∑𝑛 ∆ 𝑛 𝐻
o Follows from the fact that ∆𝐻 for a process depends only on the difference between the
final and initial states
Apple Hess’s Law as follows:
o Imagine that an overall reaction occurs through a series of individual reaction steps;
adding the steps must give the overall reaction
o Choose the individual reaction steps for which each step has a known ∆𝐻
o Add the known ∆𝐻 values for the steps to get the uknown ∆𝐻 for the overall reaction
Example: Application of Hess’s Law to the oxidation of sulfur to sulfur trioxide
1 𝑘𝐽
Equation 1: 𝑆2 (𝑠) + 𝑂2 (𝑔) = 𝑆𝑂2 (𝑔) ∆1 𝐻 = −296.8
8 𝑚𝑜𝑙
𝑘𝐽
Equation 2: 2𝑆𝑂2 (𝑔) + 𝑂2 (𝑔) = 2𝑆𝑂3 (𝑔) ∆2 𝐻 = −198.4
𝑚𝑜𝑙
1 3
Equation 3: 𝑆
8 2 (𝑠)
+ 2 𝑂2 (𝑔) = 𝑆𝑂3 (𝑔) ∆3 𝐻 = ?
1 𝑘𝐽
Equation 1: 𝑆 + 𝑂2 (𝑔) = 𝑆𝑂2 (𝑔) ∆1 𝐻 = −296.8
8 2 (𝑠) 𝑚𝑜𝑙
1 1 𝑘𝐽
½ Equation 2: 𝑆𝑂2 (𝑔) + 𝑂2 (𝑔) = 𝑆𝑂3 (𝑔) (∆2 𝐻) = −99.2
2 2 𝑚𝑜𝑙
1 3 3
Equation 3: 𝑆2 (𝑠) + 𝑆𝑂2 (𝑔) + 𝑂2 (𝑔) + 𝑂2 (𝑔) = 𝑆𝑂2 (𝑔) + 𝑆𝑂3 (𝑔)
8 2 2
1 3 𝑘𝐽
𝑆2 (𝑠) + 𝑂2 (𝑔) = 𝑆𝑂3 (𝑔) ∆3 𝐻 = −396.0
8 2 𝑚𝑜𝑙
Calculating an unknown ∆𝐻 involves three steps:
o Identify the target equation, the step whose ∆𝐻 is unknown, and note the amount (mol)
of each reactant and product
o Manipulate each equation with known ∆𝐻 values so that the target amount (mol) of
each substance is correct
Change the sign of ∆𝐻 when you reverse an equation
Multiple amount (mol) and ∆𝐻 by the same factor
o Add the manipulated equations and their resulting ∆𝐻 values
o Choose the individual reaction steps for which each step has a known ∆𝐻
Chemical kinetics: the study of how fast the change from reactants to products occurs
o Focuses on reaction rate: the change in the concentrations of reactants (or products) as
a function of time
Different reactions have different rates:
In a faster reaction (higher rate), the reactant concentration decreases quickly
In a slower reaction (lower rate), the reactant concentration decreases slowly
The rate is determined by the nature of the reactants
Any given reaction has a different rate under different conditions
Chemical processes occur over a wide range of rates (ie. Explosions vs.
ripening of fruit vs. formation of coral from dead plants)
4 factors that affect rate:
o Concentration of Reactants: Molecules must collide to react
With more molecules present, the more frequently they collide and the more
often they react
Reaction rate is proportional to the number of collisions, which depends on the
concentration of the reactants
𝑟𝑎𝑡𝑒 ∝ 𝑐𝑜𝑙𝑙𝑖𝑠𝑖𝑜𝑛 𝑓𝑟𝑒𝑞𝑢𝑒𝑛𝑐𝑦 ∝ 𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛
o Physical State of Reactants: Molecules must mix to collide
Collision frequency also depends on physical state, which determines how easily
the reactants mix
When reactants are in the same phase, as in n aqueous solution, random thermal
motion brings them into contact, but gentle stirring mixes them further
When reactants are in different phases, contact occurs only at the interface
between the phases, so vigorous stirring or even grinding may be needed
The more divided the reactant is, the greater the surface area and the more
contact it make with the other reactant, and the faster the reaction occurs
o Temperature: Molecules must collide with enough energy
Temperature affects the reaction rate by increasing the frequency and the average
energy of collisions
Frequency of collision: the most probable speed of a sample of gas is a
function of the temperature; at a higher temperature, collisions occur more
frequently, causing more molecules to react
𝑟𝑎𝑡𝑒 ∝ 𝑐𝑜𝑙𝑙𝑖𝑠𝑖𝑜𝑛 𝑓𝑟𝑒𝑞𝑢𝑒𝑛𝑐𝑦 ∝ 𝑡𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒
Energy of collisions: temperature affects the kinetic energy of the
molecules; at higher temperatures, more sufficiently energetic collisions
occur, causing more molecules to react
𝑟𝑎𝑡𝑒 ∝ 𝑐𝑜𝑙𝑙𝑖𝑠𝑖𝑜𝑛 𝑒𝑛𝑒𝑟𝑔𝑦 ∝ 𝑡𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒
o The use of a catalyst
Rate of reaction measure the change in concentrations of reactants or products per unit time
o Reactant concentrations decrease while product concentrations increase
For general reaction A B:
Measure the initial reactant concentration (𝐴1 ) at 𝑡1
Allow reaction to proceed
Measure the final reactant concentration (𝐴2 ) at 𝑡2
∆[𝐴]
o 𝑅𝑎𝑡𝑒 = − ∆𝑡
Since [𝐴2 ] must be lower than [𝐴1 ], so ∆[𝐴] is negative; the –ve sign is used to
change the reaction concentration to a +ve value for the rate
∆[𝐵]
o 𝑅𝑎𝑡𝑒 = + ∆𝑡
o If we measure the product concentrations to determine the rate, we find that [𝐵2 ] is
always higher than [𝐵1 ]; thus, ∆[𝐵] is positive
In most cases, rate varies as the reaction proceeds
o If the data points produce a curved line, it means that the rate is changing; straight
means the rate is constant
o The rate decreases over the course of the reaction because the reactant concentration
decreases over time
Average rate: change in reactant (or product) concentration over a change in time, ∆𝑡
o Slope of the line joining two points along the curve over a given period of time
o Rate slows as the reaction proceeds since the reactants are being used up
Instantaneous rate: the rate at a particular instant during the reaction
o The shorter the time period chosen, the closer to the instantaneous rate
o Slope of the line tangent to the curve that plots concentration vs. time
o Usually the term reaction rate means the instantaneous reaction rate
Initial rate: the instantaneous rate at the moment when the reactants are mixed, when t= 0
o Use this rate to avoid complication
o To find overall net rate, calculate the difference between the forward and reverse rates
o Since the initial rate is t = 0, product concentrations are negligible
The rate is exactly the opposite in terms of the product concentration because they are
increasing
The expression for the rate of a reaction and its numerical value depend on which substance
serves as reference
𝑎𝐴 + 𝑏𝐵 → 𝑐𝐶 + 𝑑𝐷
1 ∆[𝐴] 1 ∆[𝐵] 1 ∆[𝐶] 1 ∆[𝐷]
𝑅𝑎𝑡𝑒 = 𝑎 ∆𝑡 = − 𝑏 ∆𝑡 = 𝑐 ∆𝑡 = 𝑑 ∆𝑡
Rate Law (rate equation): Expresses the rate as a function of concentrations and temperature
o Based on experiment, so hypotheses about how the reaction occurs must conform to it
o For a general reaction occurring at a fixed temperature: 𝑎𝐴 + 𝑏𝐵 → 𝑐𝐶 + 𝑑𝐷
o 𝑅𝑎𝑡𝑒 = 𝑘[𝐴]𝑚 [𝐵]𝑛
𝑘 is a proportionality constant called the rate constant; specific for a given
reaction at a given temperature and does not change as the reaction proceeds
𝑚 and 𝑛 are reaction orders they define how the rate is affected by reactant
concentrations
The balancing coefficients a and b in the reaction equation are not
necessarily related in any way to the reaction orders m and n
The components of the rate law—rate, reaction orders, and rate constant—
must be found by experiment
Laboratory methods for determining the initial rate
o Spectrometric methods measure the concentration of a component that absorbs (or
emits) characteristic wavelength of light
In the reaction of NO and O2, only NO2 has colour
Known amounts of reactants are injected into a tube within a spectrometer set to
measure the wavelength and intensity of the brown colour
Since the intensity is directly proportional to the concentration of NO2, the rate
of formation of NO2 is proportional to the increase in this intensity over time
o Conductometric methods rely on the change in the electrical conductivity of the
reaction solution when nonionic reactants form ionic products, or vice versa
The HBr that forms is a strong acid that can dissociate completely in water
As time passes, more ions form so the conductivity of the reaction mixture
increases
o Manometric methods employ a manometer attached to a reaction vessel of fixed
volume and temperature
The rate of reaction is directly proportional to the increase in H2 gas pressure
A reaction has an individual order with respect to each reactant, as well as an overall order
(the sum of the individual orders)
o For the reaction 𝐴 → products:
o First order: if the rate doubles when [A] doubles, the rate depends on [A] raised to the
first power, [𝐴]1
𝑅𝑎𝑡𝑒 = 𝑘[𝐴]1 = 𝑘[𝐴]
o Second order: if the rate quadruples when [A] doubles, the rate depends on [A]
squared, [𝐴]2
𝑅𝑎𝑡𝑒 = 𝑘[𝐴]2
o Pseudo first order: a reaction can also be second order if it is first order in two different
reactants A and B
𝑅𝑎𝑡𝑒 = 𝑘[𝐴]1 [𝐵]1 = 𝑘[𝐴][𝐵]
In these situations, second-order reactions might appear to be first order in an
experiment
Generally occurs if the amount of one of the reactants in the reaction mixture
greatly exceeds the amount of the other reactant
The concentration of one seems to change by a lot, while the other only
experiences small changes
When [𝐵] ≫ [𝐴], 𝑅𝑎𝑡𝑒 = 𝑘[𝐵] ∙ [𝐴] = 𝑘′[𝐴]
Reaction now appears to be first order since [B] is essentially a constant and has
been incorporated into the value of k, creating a new rate constant, k’
o Zero order: if the rate does not change when [A] changes, the rate does not depend on
[A]
𝑅𝑎𝑡𝑒 = 𝑘[𝐴]0 = 𝑘(1) = 𝑘
Integrated Rate Laws: can include time as a variable to the rate law
o Used to find either the time needed to reach a certain concentration of reactant or the
concentration present after a given time
∆[𝐴]
𝑅𝑎𝑡𝑒 = − ∆𝑡
and 𝑅𝑎𝑡𝑒 = 𝑘[𝐴]
∆[𝐴]
𝑘[𝐴] = − ∆𝑡
∆[𝐴]
𝑘∆𝑡 = −
[𝐴]
[𝐴]0
ln = 𝑘𝑡 (first order reaction; 𝑅𝑎𝑡𝑒 = 𝑘[𝐴])
[𝐴]𝑡
𝑙𝑛[𝐴]𝑡 = −𝑘𝑡 + ln[𝐴]0 (y=mx+b)
1 1
− [𝐴] = 𝑘𝑡 (second order reaction; 𝑅𝑎𝑡𝑒 = 𝑘[𝐴]2 )
[𝐴]𝑡 0
1 1
= 𝑘𝑡 + [𝐴] (y=mx+b)
[𝐴]𝑡 0
[𝐴]𝑡 − [𝐴]0 = 𝑘𝑡 (zero order reaction; 𝑅𝑎𝑡𝑒 = 𝑘)
[𝐴]𝑡 = −𝑘𝑡 + [𝐴]0 (y=mx+b)
Straight line when plotting ln[reactant] vs. t, the reaction is first order
Straight line when plotting 1/[reactant] vs. t, the reaction is second order
Straight line when plotting [reactant] vs. t, the reaction is zero order
Half-life (𝑡1/2 ): the time that the reactant concentration takes to reach half its initial value
o First Order Reactions
[𝐴]
Ln [𝐴]0 = 𝑘𝑡
𝑡
[𝐴]0
ln 1 = 𝑘𝑡1/2 or 𝑙𝑛2 = 𝑘𝑡1/2
[𝐴]0
2
𝑙𝑛2 0.693
𝑡1/2 = = (first order process; 𝑅𝑎𝑡𝑒 = 𝑘[𝐴])
𝑘 𝑘
For a first-order reaction, half-life is constant and independent of the reactant
concentration
o Second Order Reactions
1
𝑡1/2 = 𝑘[𝐴] (second order process; 𝑅𝑎𝑡𝑒 = 𝑘[𝐴]2 )
0
In contrast to the first-order reaction, the half-life of the second-order reaction
depends on reactant concentration
The half-life is inversely proportional to the initial reactant concentration
o Zero Order Reactions
[𝐴]
𝑡1/2 = 2𝑘0 (zero order process; 𝑅𝑎𝑡𝑒 = 𝑘)
In contrast to the second-order reaction, the half-life of the zero-order reaction is
directly proportional to the initial reactant concentration
14.5 Theories of Chemical Kinetics
Collision Theory: particles must collide to react, and the number of possible collisions is
found by multiplying the number of reactant particles
o Particles—atoms, molecules, or ions—must collide to react
o However, the number of collisions is not the sole factor that determines rate
o Collision frequency provides an upper limit on how fast a reaction can occur
o Concentrations are multiplied in the rate law since the laws of probabilities states that
the number of collisions depends on the product of the number of reactant particles
o Arrhenius equation: 𝑘 = 𝐴𝑒 −𝐸𝑎 /𝑅𝑇
Where k is the rate constant, e is the base of the natural log, T is the absolute
temperature and R is the universal gas constant
T is the denominator of a negative exponent: as T increases, the value of the
negative exponent becomes smaller, meaning k becomes larger
Higher T larger k increased rate
o Activation energy (𝐸𝑎 ): an energy threshold that the colliding molecules must exceed
in order to react
Relative values for forward and reverse reactions depend on whether the overall
reaction is exothermic or endothermic
A reversible reaction has two activation energies: the activation energy for the
forward reaction, 𝐸𝑎(𝑓𝑤𝑑) and the activation energy for the reverse reaction
𝐸𝑎(𝑟𝑒𝑣)
∆𝑟 𝐻 = 𝐸𝑎(𝑓𝑤𝑑) − 𝐸𝑎(𝑟𝑒𝑣)
o A rise in temperature has two effects on moving particles:
Collision frequency- if particles move faster, they collide more often
Collision energy- the effect on temperature on collision energy is a major factor
𝑓 = 𝑒 −𝐸𝑎 /𝑅𝑇
A rise in temperature enlarges the fraction of collisions with enough energy
to exceed 𝐸𝑎
o The smaller the activation energy (or the higher the temperature), the larger the fraction
of sufficiently energetic collisions, the larger the value of k and the higher the reaction
rate are:
Smaller 𝐸𝑎 (or higher T) larger f larger k higher rate
𝑘 = 𝐴𝑒 −𝐸𝑎 /𝑅𝑇
𝐸𝑎 1
ln 𝑘 = ln 𝐴 − ( )
𝑅 𝑇
𝑘2 𝐸𝑎 1 1
ln 𝑘 = − 𝑅
(𝑇 − 𝑇 )
1 2 1
Effective collisions- To have an effective collision, molecules must collide with enough
energy and the appropriate molecular orientation
𝑘 = 𝐴𝑒 −𝐸𝑎 /𝑅𝑇 , where A is the pre-exponential factor, the product of the collision frequency
(Z) and an orientation probability factor (p), which is specific to each reaction
o 𝐴 = 𝑝𝑍
o The more complex the structure, the smaller the p value
o Individual atoms are spherical, so the p values are near 1: as long as reacting atoms
collide with enough energy, the product forms
Transition State Theory: focuses on the change of kinetic energy to potential energy as
reactant particles collide and form an unstable transition state
o As molecules approach each other, repulsions between electron clouds increase so they
slow as some of their kinetic energy is converted to potential energy
o If the energy of the collision is less than the activation energy, the molecules bounce
off of each other
o For the fraction of collisions with fast moving molecules, their kinetic energies push
them together with enough force to overcome the repulsions and surpass the activation
energy
o At some point, there is a species with partial bonds that is neither reactant nor product
o Transition State (activated complex): unstable species that exists only at the instant of
highest potential energy
The activation energy of a reaction is used to reach the transition state
Reaching the transition state does not guarantee that the reaction will proceed,
because a transition state can change in either direction
Transition state theory proposes that every reaction (or step in an overall reaction) goes
through its own transition state
Reaction energy diagram plots how potential energy changes as the reaction proceeds from
reactants to products (the reaction progress)
Reaction mechanism: a sequence of single reaction steps that sum to the overall equation
o Chemists propose a mechanism/hypothesis and test it to see if it fits with the observed
rate law
Elementary reactions: individual steps that make up a reaction mechanism
o Each describes a single molecular event
One particle decomposing
Two particles combining
Molecularity: the number of reactant particles in the step
o Unimolecular reaction: a reaction that involves the decomposition or rearrangement of
a single particle
o Bimolecular reaction: a reaction in which two particles react
o Termolecular elementary steps occur, but are extremely rare due to low probability
o In general, unimolecular and/or bimolecular reactions are reasonable steps in a
mechanism
Since an elementary reaction occurs in one step, its rate law can be deduced from the reaction
stoichiometry: reaction order equals molecularity
o Only for an elementary step, we use the equation coefficients as the reaction orders in
the rate law
Rate-Determining Step: a slow step that limits how fast the overall reaction can proceed
o The rate law of the rate-determining step become the rate law for the overall reaction
o Reaction Intermediate: a substance that is formed and used up during the reaction
Although it does not appear in the overall balanced equation, a reaction
intermediate is essential for the reaction to occur
Intermediates are less stable than the reactants and products, but unlike the much
less stable transition states, they have normal bonds and can sometimes be
isolated
Key points about this mechanism
o If k1 = k, the rate law for the rate-determining step (step 1) becomes identical to the
observed rate law
o Because the first step is slow, as soon as any intermediate is formed it is consumed by
the fast second step, so the reaction takes as long as the first step does
o Something that takes part after the rate-determining step has a reaction order of 0
A valid mechanism must meet three criteria:
o The elementary steps must add up to the overall balanced equation
o The elementary steps must be reasonable (they should generally involve one reactant
particle or two)
o The mechanism must correlate with the rate law, not the other way around
Steady-Step Approximation: use of an intermediate in the mechanism to determine the rate
law