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Increasing the concentration of each reactant (increasing the number of moles of reactant per liter of solution).
Youll determine the rate of a reaction by measuring the decrease in reactant concentration over a period of time
(as it is being converted into product). Youll then need to make a conclusion as to whether reaction rate increases
or decreases when the concentration of each reactant is increased, and when the overall temperature of the reaction
is increased.
The change in mass as the bubbles of oxygen gas diffuse out of the reaction flask provides a way to measure how
quickly the product is being formed. The graph to the right shows the increase in oxygen concentration (as well as
the decrease in hydroxide peroxide concentration) over a period of time.
1L
C. Graham Brittain
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Chemical reactions can only occur when the reactant molecules or ions collide with one another. This idea is
referred to as the Collision Theory of Chemical Kinetics:
In order for reactant particles (atoms, ions, or molecules) to react, they must
collide.
The collision energy must be greater than or equal to the Activation Energy (Ea)
in order to have an effective (successful) collision one that has sufficient energy
to break key bonds and rearrange the atoms.
The Activation Energy (Ea) is the minimum energy that must be supplied by the
collision in order for the reaction to occur by a particular pathway. It is the
difference between the energy level of the reactants and the energy level of the
transition state (the intermediate that exists at the moment of collision, when
the kinetic energy, converted into collision energy, is used to break bonds and
rearrange the atoms).
A certain fraction of all molecules in a sample will have the necessary Activation
Energy to react, and that fraction will increase with increasing temperature.
Not every molecular collision can be effective or successful, in that it leads to the breaking of bonds in the
reactant molecules and the formation of new bonds in the product molecules. In fact, the result of many collisions
is that the molecules simply bounce apart without reacting.
Only molecules that collide with sufficient energy (to break the bonds) and with the correct orientation (to
exchange atoms) will have an effective (successful) collision that leads to the formation of products.
There are four factors that can influence the rate of a chemical reaction:
1. The Ionic or Molecular Nature of the Reactants
In general, chemical reactions that occur between
ions in aqueous solution are extremely rapid: they
happen almost instantaneously when the solutions
containing the reacting ions are mixed. This is
because the attractive forces between the ions (the
ionic bonds) are broken as the compound dissolves
and the ions become hydrated by the water molecules
(as you learned in last weeks experiment).
Additionally, most ions exert attractive forces
equally in all directions. There is no preferred
orientation for collision, and usually no covalent
bonds need to be broken (unless the ions are
polyatomic).
In contrast, reactions between molecules (that require
covalent bonds to be broken or formed) tend to
proceed much more slowly. Certain structural
characteristics of the reactant molecules, such as
bond polarity, geometry, overall size, and orientation
will influence the reaction rate as well.
C. Graham Brittain
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C. Graham Brittain
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You may remember from last weeks solubility experiment that potassium permanganate dissolves in water to
yield an intensely purple-colored solution. Youll use this purple color to monitor how quickly the permanganate
ion reacts with oxalic acid.
As the permanganate ion is used up by this reaction, the purple color will fade to red, and then to a yellow-brown.
This color change will signal that the reaction has gone to completion, and that the permanganate ion has been
used up (its concentration has reached 0 moles/liter).
To establish the reaction rate, youll measure the amount of time that elapses between the mixing of the reactants
and the disappearance of the permanganate ions purple color.
The rate of the reaction can be calculated by the following equation:
=
The symbol in the equation above means change in, and the square brackets around the chemical formula
for potassium permanganate means concentration of in Molarity units (of moles/liter).
So the reaction rate is calculated by dividing the change in the permanganate ion concentration by the elapsed
time.
But the change in the permanganate concentration is simply the difference between the initial concentration (at the
start of the reaction) and the final concentration (at the end of the reaction). And as discussed above, the final
concentration is assumed to be 0 moles/liter (when the disappearance of the purple color signals that the reaction
has gone to completion).
Thus the change in concentration will be the same numerical value as the initial concentration.
And the change in time is simply the number of seconds that elapses from the start of the reaction at time zero
(when the reactant solutions are mixed) until the purple color has faded to yellow-brown.
Thus the rate equation simplifies to:
=
As mentioned above, youll study the effects of concentration and temperature on the rate of this reaction.
Effect of Concentration:
Youll conduct a series of experiments in which the concentration of one reactant will be varied, while the
temperature and concentration of the second reactant will be held constant.
Effect of Temperature:
Youll conduct a series of experiments in which only the temperature of the reaction will be varied, while
the concentration of all reactants will be held constant.
For each set of reaction conditions, you must determine the initial permanganate concentration and the elapsed
time in order to determine the rate of the reaction.
C. Graham Brittain
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A. Experimental Set-up
1. Dispense 5.0 ml of the oxalic acid solution (H2C2O4) from the pump bottle into a labeled 4 test tube. Record
the concentration of the H2C2O4 solution in moles/liter (M).
2. Dispense 5.0 ml of the potassium permanganate solution (KMnO4) from the pump bottle into a second labeled
4 test tube. Record the concentration of the KMnO4 solution in moles/liter (M).
3. Add approximately 5.0 mL of distilled water to a third labeled 4 test tube.
4. Place all three test tubes in your rack. Note that it is essential to label the tubes, as both the distilled water and
oxalic acid solution are colorless, and could easily be confused. Place a Beral pipet in each test tube for
measuring drop size quantities of each reagent.
Distilled water
6 drops
1 drop
5 drops
H2C2O4 solution
5 drops
10 drops
5 drops
KMnO4 solution
1 drop
1 drop
2 drops
12 drops
12 drops
12 drops
Total Volume
4. Dispose of the used solution in a waste beaker at your lab bench. Rinse and dry the reaction test tube.
5. Record the temperature of the remaining distilled water in the stock supply test tube. Youll assume that this is
the temperature at which all three trials of all three experiments were conducted. The three trails of
Experiment 1 will also serve as your room temperature data for Part C.
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possible to avoid the loss of heat. Then, at the instant that the purple color has faded (from red, and then) to
yellow-brown, the elapsed time in seconds must be recorded.
5. Dispose of the used solution in the waste beaker at your lab bench. Rinse and dry the reaction test tube.
Repeat steps 3 and 4 to conduct two more trials of the experiment at this temperature
6. Add ice to the warm water bath to reduce its temperature to 20-22oC above room temperature. Hold the
temperature constant as you did in step 1 above. Follow the same procedure that you did in steps 2 through 5,
to conduct a total of three trials of the experiment at this temperature.
7. Add ice to the warm water bath to reduce its temperature to 10-12oC above room temperature. Hold the
temperature constant as you did in step 1 above. Follow the same procedure that you did in steps 2 through 5,
to conduct a total of three trials of the experiment at this temperature.
D. Calculation of Results
1. Realize that when the KMnO4 solution was added to the distilled water and H2C2O4 mixture, it was diluted
from its original stock concentration by the volumes of water and oxalic acid solution. That means youll need
to calculate the concentration of KMnO4 that was present in the reaction test tube at the instant the reaction
began. This requires use of the dilution formula you learned in your lecture course:
=
In this formula:
C1 is the stock concentration of KMnO4
V1 is the volume of KMnO4 added to the distilled water and H2C2O4 mixture.
V2 is the total volume of solution in your reaction test tube (the volumes of distilled water, H2C2O4, and
KMnO4).
When these substitutions are made, and the dilution formula is rearranged to solve for C2, the result is:
= =
#
#
2. Finally, youll calculate the Average Rate of Reaction for EACH Experiment:
=
Note that for the Effect of Concentration study (part B of the procedure), youll calculate the Average Rate of
Reaction for EACH of the three Experiments, using
The average elapsed time (the average time of reaction from the three TRIALS you ran for each
EXPERIMENT).
And note that for the Effect of Temperature study (part C of the procedure), youll calculate the Average Rate
of Reaction at EACH of the three Temperatures, using
The [KMnO4]initial (which was held constant for all trials at all temperatures)
The average elapsed time (the average time of reaction from the three TRIALS you ran at each
TEMPERATURE).
C. Graham Brittain
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________________________________
________________________________
Effect of Concentration
Experiment 1:
Drops of Distilled Water
Drops of H2C2O4
Drops of KMnO4
Trial 1
Trial 2
Trial 3
Experiment 2:
Drops of Distilled Water
Drops of H2C2O4
Drops of KMnO4
Trial 1
10
Trial 2
10
Trial 3
10
Experiment 3:
Drops of Distilled Water
Drops of H2C2O4
Drops of KMnO4
Trial 1
Trial 2
Trial 3
C. Graham Brittain
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Effect of Temperature
Temperature 4 (30-32 oC > room temperature): _________________________
Drops of Distilled Water
Drops of H2C2O4
Drops of KMnO4
Trial 1
Trial 2
Trial 3
Drops of H2C2O4
Drops of KMnO4
Trial 1
Trial 2
Trial 3
Drops of H2C2O4
Drops of KMnO4
Trial 1
Trial 2
Trial 3
Drops of H2C2O4
Drops of KMnO4
Trial 1
Trial 2
Trial 3
C. Graham Brittain
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#
#
Experiment 1:
Experiment 2:
Experiment 3:
Experiment 1:
Experiment 2:
Experiment 3:
C. Graham Brittain
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#
#
C. Graham Brittain
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Discussion Questions
1. In the Effect of Concentration study, compare your procedure and results for Experiments 1 and 2.
a) Which reactant concentration was increased (KMnO4 or H2C2O4)? ________________________________________
How much was it increased (doubled, tripled, quadrupled)? ________________________________________
Which reactant concentration was held constant (KMnO4 or H2C2O4)? ___________________________________
b) How did this increase in reactant concentration affect the rate of reaction (no effect, doubled, tripled, quadrupled)?
_______________________________________
c) Is this result consistent with your expectation? Explain.
(Recall that for many reactions there is a direct relationship between concentration and rate: when the
concentration of a reactant is doubled, the rate is also doubled.)
2. In the Effect of Concentration study, compare your procedure and results for Experiments 1 and 3.
a) Which reactant concentration was increased (KMnO4 or H2C2O4)? ________________________________________
How much was it increased (doubled, tripled, quadrupled)? ________________________________________
Which reactant concentration was held constant (KMnO4 or H2C2O4)? ___________________________________
b) How did this increase in reactant concentration affect the rate of reaction (no effect, doubled, tripled, quadrupled)?
_______________________________________
c) Is this result consistent with your expectation? Explain.
(Recall that for many reactions there is a direct relationship between concentration and rate: when the
concentration of a reactant is doubled, the rate is also doubled.)
C. Graham Brittain
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3. What would be your estimate of the reaction TIME (number of seconds required for the purple color to
disappear) if you reacted 1.5 drops of KMnO4 with 5 drops of H2C2O4? Explain your reasoning.
(Realize that the # of drops of water would be adjusted so that the total volume of solution would still be 12 drops.)
4. What effect did increasing the temperature have on the RATE of this reaction?
Did the change in rate match the rule of thumb (each time the temperature is increased by 10oC, the rate of the
reaction doubles)?
Explain your results.
5. What would be your estimate of the reaction RATE if you decreased the temperature by 10oC by allowing the
reaction test tube to cool in an ice-water bath?
(Think through this Would the time required for the reaction be longer or shorter? And how would that affect
the rate?) Explain your reasoning.
C. Graham Brittain
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