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Transcript of Rates of reactions
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RATES O
F REACTI
ONS
TO
PI C
6
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6.1 DETERMINING THE RATE OF A CHEMICAL RXN
What is the rate of a chemical rxn?
The speed at which reactants are used up and products are formed
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EXPERIMENTS TO MEASURE RATE OF RXN
Consider this rxn:
CaCO3(s) + 2HCl(aq) CaCl2(aq) + CO2(g) + H2O
We can measure the rate of rxn in 2 ways1.Measure rate that CO2 is produced
2.Measure the rate at which the mass decreases
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MEASURING CO2 PRODUCTION
HCl(aq)
CaCO3(s)
Delivery Tube
Water
Measuring Cylinder
CO2(g)
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MEASUREMENT OF THE RATE MASS DECREASES
Mass decreases as CO2 is given off
Measure mass decrease every 10 sec
Plot the data
HCl(aq)
CaCO3(s)
Balance
Cotton Wool
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RATE OF RXN DEFINED
Change in concentration of reactants or products per unit of time
(Time could be 1 sec, 1 min, etc)Average rate= (change in
concentration)/(time)Unit are dm-3 s-1, dm-3 min-1, etcIf a given amount of reactant is used up,
the same amount will be produced
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6.2 COLLISION THEORY
What is the product of particles colliding?Reactions
For collisions to result, there are two conditions that must be fulfilled
1. Collision must involve more than a certain minimum amount of energy
2. Molecules must collide with the correct orientations
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COLLISION MUST INVOLVE A CERTAIN MIN. AMOUNT OF ENERGY
To react, particles must collide with sufficient energy
The min. energy must result in the activation energy (Ea)
Ea is the minimum amount of energy that colliding particles must posses for a collision to result in a rxn
If particles collide and do not overcome Ea, they will just bounce off each other
Collisions resulting in a reaction are called successful or effective collisions
Not all rxns that overcome Ea will result in rxn
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MOLECULES COLLIDE WITH CORRECT ORIENTATION
If molecules do not collide with correct orientation they will not react
Main factors affecting rate of rxn
1. Concentration of reactants
2. Pressure for reactions involving gases
3. Surface area of solid reactants
4. Temperature
5. Catalysis
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EFFECTS OF CONC.
Does higher reactant concentrations, how will it effect the rate?
With more particles in a given volume, there will be more collisions
Increases the chances of successful collisions
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EFFECTS OF PRESSURE
How will increased pressure effect rate?
Similar to concentration increase
Increases collision frequency
Only reactions involving gases are significantly affected by changing pressure
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EFFECT OF SURFACE AREA OF SOLID REACTANTS
Reactions generally only occur on the surface of solids
How can surface area of a solid be increase?
Finely divide the solid to open up more areas for
reactions
Allows for more potential collision opportunities
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RELATIONSHIP BETWEEN TEMP AND THE ENERGY OF PARTICLES IN A GAS
How does temp effect the movement of particles?
Ideal gas: kinetic energy of the particles in a gas is
proportional to its temp in K
If temp is doubled, average energy is generally
doubled
Does not depend on identity of gas, however lighter
molecules will be traveling faster than heavier
ones
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EFFECTS OF TEMP ON RATE
How does temp effect rate?
The rate will generally double for every 10 K increase in
temp
Why?
Collision frequency increases due to particles moving faster
The also collide harder
Increases the chance for collision
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MAXWELL-BOLTZMANN
Distribution of molecular kinetic energies at a particular temp
Only a few particles with high energy and only a few low energy
Most particles have average energy
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CATALYSIS
Catalyst A substance that increases the rate of a
chemical rxn without itself being used up in the rxn
Often written above the yield arrow in the equation
Also allow the rxn to proceed by an alternative
pathway of lower activation energy
May be homogeneous (same state as reactants) or
heterogeneous
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HL2
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6.3 THE RATE EXPRESSION
Rate equation/ expression
Consider A B
Rate is directly proportional to [A]
Rate= k[A]
k is the rate constant
The rate expression is experimentally determined equation relating to the rate of rxn to the concentration of substances in the rxn mixture
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RATE EXPRESSION
General equation
xA + yB C + D
Rate= k[A]m[B]n
Rate constant a constant of proportionality relating the concentrations in the experimentally determined rate expression to the rate of the rxn
Only constant at a particular temp
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ORDER OF RXN
In respect to a particular reactant is the power
of the reactant’s concentration in the
experimentally determined rate equation
m and n are the orders of the reactants
Overall order is m+ n
Rate expression can be determined
experimentally
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EXPERIMENTAL DETERMINATION OF RATE EXPRESSION
Consider, A + B CThe initial rate can be taken because
we know the initial concentrations of A and B
An experiment with a fixed amount of B and varied concentrations of A is performed
Then do the same with fixed A and varied B
Use data to determine orders of A and B
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DETERMINING ORDER OF REACTION AND RATE EXPRESSION FROM EXPERIMENTAL DATA
Given the reaction 2A B
Experiment
[A]/ mol dm-3
Rate/ mol dm-3 s-1
1 1.0 0.60
2 2.0 1.2
3 5.0 3.0
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CONT
We want to determine:1.The order with respect to A2.The rate expression3.The value of the rate constant (w/
units)4.The rate of reaction when [A]=
1.3 mol dm-3
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ZERO-ORDER RXNS
Rate independent of concentrationRate equation is: rate=kUnits of k are conc. time-1
Could be mol dm-3 s-1
mol dm-3 h-1
etc.
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FIRST –ORDER RXNS
Rate is directly proportional to the concentration
Half- life is first-order
Half-life is related to rate constant:
rate constant= 0.693/ half-life
Rate equation: rate=k[A]
Units of k are time-1
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SECOND-ORDER RNS
Rate of rxn is proportional to concentration squared
Rate expression: rate=k[A]2
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UNITS OF RATE CONSTANT
Overall order
Units of k Example of units
0 Concentration time-1
mol dm-3 s-1
1 time-1 s-1
2 Concentration-1
time-1
mol-1 dm3 s-1
3 Concentration-2
time-1
mol-2 dm6 s-1
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6.4 THE ARRHENIUS EQUATION
Shows the variation of the rate constant with temperature
As temp. increases, the rate constant increases exponentially
Equation: k=Ae-Ea/RT
A pre-exponential factor, A-factor or frequency factor
Relates to frequency and orientation of collision
A constant that varies slightly with temperature
e-Ea/RT the fraction of collision where E> Ea (Energy is greater than activation energy)
Not all reactions where E> Ea will result in collision
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THE OTHER ARRHENIOUS EQUATION
May also be written as lnk= (-Ea/R) x (1/T) + lnA
This form is used to solve for activation energy, if these procedures are followed
1. Conduct a series of temperature-varied experiments
2. Calculate rate constant for each temp.
3. Plot a graph of lnk (y-axis) vs. 1/T (x-axis)
Temp in K
Slope = -Ea/R (R= gas constant)
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EFFECTS OF A CATALYST ON RATE CONSTANT
If the rate equation is: rate= k[A][B]
Catalyst increases rate constant
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6.5 MECHANISMS OF REACTIONS
Consider the reaction, 2NO2(g) +F2(g) 2NO2F(g)
If this rxn were to occur in a single step, all 3 molecules would have to collide in correct orientation at the same time
We could assume that if the concentration was increased the chances of proper collision would increase
This makes the rate dependent upon reactant concentrations
Rate equation will be: rate= [NO2]2[F2]
The 2 superscript comes from the coefficient in the balanced equation
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CON’TThe rate derived from experimentation was
found to be
rate= [NO2][F2]
This suggests that the rxn does not occur in a single step
Thus, this reaction (as many more) must occur in multiple steps
The chances of molecules colliding in perfect orientation simultaneously is quite low
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SUGGESTEDMECHANISMS OF THIS RXN
NO2 + F2 NO2F +F Step 1
NO2 + F NO2F Step 2
2NO2 + F2 2NO2F Overall Equation
Step 1:rate= k1[NO2][F2]
Step 2:rate= k2[NO2][F]
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CON’T
Step 1 is the same as the overall equation, thus must be the step determining the rate for the overall rxn
Called the rate-determining step (the slow step)
Step 2 is the fast step and does not influence the overall rate of rxn to a great extent
thus, the concentrations of the step species are not included in the rate equation
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GENERIC EXAMPLE
A + 2B C
B + B Q Step 1 rate- determining step
Q + A C Step 2 fast
Mechanism
B + B Q
Q + A C
2B + A C
Thus, rate= k[B]2 since it is the only species remaining from the first step
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RATE DETERMINING STEP AS SECOND STEP
B + B Q Step 1 fast
Q + A C Step 2 rate-determining step
Process of determining overall rate is basically the same as if the first step as the slow step
Rate= k[Q][A]
Because Q is produced by 2 B molecules in the first step, we can replace [Q] with [B]2
Rate= k[B]2[A]
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ANOTHER MECHANISM
A + B S step 1 fast
S + B C step 2 rate-determining step
Reactants involved up to and including the rate determining step are included in rate equation
Rate= k[B]2[A]
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REACTION INVOLVING A CATALYST
CH3COCH3(aq) + I2(aq) CH3COCH2I(aq) + HI(aq)
The rxn is acid (H+) catalysed
Experimental rate expression is
Rate= k[CH3COCH3][H+]
Does not include I2, so it is only involved after the rate-determining step
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CON’T
Proposed mechanism:
CH3COCH3 + H+ X rate-determining step
X + I2 CH3COCH2I + HI + H+ fast
Catalyst is involved in the rate- determining step but is regenerated in second step and does not appear in the overall chemical equation
X is an intermediate
H+ cancels out
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SN1 VS SN2 MECHANISMS
(CH3)3CBr + OH- (CH3)3COH + Br –
This is a nucleophilic substitution
Experimental rate expression: rate= k[(CH3)3CBr]
Since OH- is not included, it is in the fast step
Suggested mechanism:
(CH3)3CBr (CH3)3C+ + Br – rate- determining step
(CH3)3C+ + OH- (CH3)3COH fast
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CON’T
This is considered SN1
S= substitution
N= nucelophilic
1= molecularity of rate- determining step
Molecularity # of ‘molecules’ that react in a particular step (usually rate-determining)
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SUMMARY OF MECHANISM RULES
1. Mechanism must agree with overall stoichiometric equation
2. Maximum of 2 particles can react in any one step
3. All species in rate equ. Must appear in mechanism in or before the rate-determining step
4. The power of a particular reactant’s concentration in the rate equ. Indicates the # of times it appears in the mechanism up to and including the rate determining step