5.4 - Worked Example
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Understanding Rate Expressions
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Today, we are going to talk about rate expressions! Can anyone tell me why determining a rate expression is important in chemical kinetics?
Isn't it because it helps us understand how the rate of a reaction depends on the concentration of the reactants?
Exactly, great point! The rate expression shows how the rate is affected by the concentrations of reactants. Now, if we have a reaction like A + B β Products, how do we find this expression?
Do we take the initial concentrations from experiments?
Yes! We conduct experiments with varying initial concentrations and measure the initial rates. Let's remember to compare these experiments effectively. One way to think about it is the acronym 'CRA' which stands for 'Compare, Rate, Analyze'!
What do we do after we compare the data?
Good question! After comparison, we deduce the order of the reaction with respect to each reactant. Can anyone describe what 'reaction order' means?
It's the exponent in the rate equation that tells us how the reaction rate changes with concentration!
Exactly right! Remember, the sum of all orders gives us the overall order of the reaction.
To summarize, always begin the process by collecting data, comparing, and analyzing to determine the rate expression!
Using Experimental Data
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Let's look at our experimental data now! In Experiment 1, we have [A] = 0.10 and [B] = 0.10, with a rate of 2.0 x 10^-3. Who can help me find the order with respect to A from Experiments 1 and 2?
When we compare Experiment 1 and Experiment 2, [A] doubles, and the rate doubles too! So, itβs first order with respect to A!
Exactly! Now, when we look at the comparison between Experiment 1 and Experiment 3, what do we notice?
The concentration of B doubles, and the rate quadruples, which means it's second order with respect to B!
Great teamwork, everyone! So, we can express the rate expression as Rate = k [A][B]^2. What should we do next?
Calculate the rate constant k using one of the experiments!
Correct! Letβs plug the values from Experiment 1 into the equation to find k. Can someone remind me how we set that up?
We rearranged the equation to solve for k using Rate = k [A][B]^2.
Absolutely! We determined that k = 2.0 mol^-2 dm^6 s^-1. Excellent work identifying the rate expression!
Practice Rate Calculations
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Now that you understand the calculations, letβs practice! I've got more data for you: Experiment 1 with [A]= 0.05, [B]= 0.1, and a rate of 1.0 x 10^-3. Experiment 2 with [A]= 0.1, [B]= 0.1, result in 2.0 x 10^-3. What can we conclude about the order for A?
If A doubles and the rate doubles, it's first order with respect to A!
Excellent! Now suppose we change Experiment 1 conditions to [A]= 0.05 and [B]= 0.2 giving a rate of 2.0 x 10^-3. What do we deduce about B?
If we doubled B and got four times the rate, then itβs second order with B as well!
Exactly! So how would we express our new rate equation?
Rate = k [A][B]^2!
Excellent! Lastly, if we used these rates to calculate k, make sure to share your solutions with the class. Remember, accuracy matters!
Introduction & Overview
Read summaries of the section's main ideas at different levels of detail.
Quick Overview
Standard
In this section, we analyze a hypothetical chemical reaction, A + B β Products, and use given experimental initial rate data to determine the rate expression and rate constant. The process involves comparing experiments to derive the reaction order with respect to each reactant, resulting in a complete rate expression and calculated rate constant.
Detailed
Worked Example
In this section, we delve into a practical demonstration of the principles discussed in earlier sections regarding chemical kinetics, rates of reactions, and rate expressions. We will focus on a hypothetical reaction represented as A + B β Products. By examining provided initial rate data from multiple experiments, we will identify the order of the reaction with respect to each reactant and calculate the rate constant.
Experimental Rate Data
| Experiment | Initial [A] (mol dm$^{-3}$) | Initial [B] (mol dm$^{-3}$) | Initial Rate (mol dm$^{-3}$ s$^{-1}$) |
|---|---|---|---|
| 1 | 0.10 | 0.10 | 2.0 x 10$^{-3}$ |
| 2 | 0.20 | 0.10 | 4.0 x 10$^{-3}$ |
| 3 | 0.10 | 0.20 | 8.0 x 10$^{-3}$ |
Determine the order with respect to [A]
To analyze the reaction order with respect to [A], we compare Experiment 1 and Experiment 2. In these experiments, the concentration of B remains constant while A doubles from 0.10 to 0.20 mol dm$^{-3}$.
- The initial rate doubles from 2.0 x 10$^{-3}$ to 4.0 x 10$^{-3}$ mol dm$^{-3}$ s$^{-1}$.
- Therefore, since a doubling in [A] leads to a doubling in rate, the reaction is first order with respect to A (m=1).
Determine the order with respect to [B]
Next, we compare Experiment 1 and Experiment 3. Here, the concentration of A is kept constant, while B doubles from 0.10 to 0.20 mol dm$^{-3}$.
- The initial rate quadruples from 2.0 x 10$^{-3}$ to 8.0 x 10$^{-3}$ mol dm$^{-3}$ s$^{-1}$.
- This means doubling [B] results in a quadrupling of rate, indicating the reaction is second order with respect to B (n=2).
Complete Rate Expression
Based on our findings, the complete rate expression for the reaction can now be established as:
$$Rate = k [A]^1 [B]^2$$
This can be simplified to:
$$Rate = k [A] [B]^2$$
Calculation of Rate Constant (k)
We can use the data from any experiment to calculate the rate constant. Choosing Experiment 1:
$$2.0 x 10^{-3} = k imes (0.10) imes (0.10)^2$$
This rearranges to:
$$k = \frac{2.0 x 10^{-3}}{0.0010} = 2.0 ext{ mol}^{-2} ext{ dm}^{6} ext{ s}^{-1}$$
Thus, the calculated rate constant for the reaction is k = 2.0 mol$^{-2}$ dm$^{6}$ s$^{-1}$.
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Experimental Data Overview
Chapter 1 of 5
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Chapter Content
| Experiment | Initial [A] (mol dm$^{-3}) | Initial [B] (mol dm$^{-3}) | Initial Rate (mol dm$^{-3} s^{-1}) |
|---|---|---|---|
| 1 | 0.10 | 0.10 | 2.0 x 10$^{-3}$ |
| 2 | 0.20 | 0.10 | 4.0 x 10$^{-3}$ |
| 3 | 0.10 | 0.20 | 8.0 x 10$^{-3}$ |
Detailed Explanation
This chunk presents experimental data used to determine the rate expression for a hypothetical reaction involving reactants A and B. The data includes varying initial concentrations of A and B across three experiments, along with the corresponding initial reaction rates. Each experiment is carefully designed to isolate the effect of changing one reactant concentration while keeping the other constant.
Examples & Analogies
Think of these experiments like adjusting the volume of two ingredients in a recipe to see how each affects the taste of a dish. By changing one ingredient while keeping another the same, we can identify how each one contributes to the overall flavor.
Determining Order with Respect to [A]
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Chapter Content
To determine the order with respect to [A]:
- Compare Experiment 1 and Experiment 2. In these two experiments, the initial concentration of B is kept constant (0.10 mol dm$^{-3}), while the initial concentration of A doubles (from 0.10 to 0.20 mol dm$^{-3}).
- Observe the change in initial rate: The rate doubles (from 2.0 x 10$^{-3}$ to 4.0 x 10$^{-3}$ mol dm$^{-3} s^{-1}$). Since a doubling in [A] resulted in a doubling of the rate (2^m = 2), the reaction is first order (m=1) with respect to A.
Detailed Explanation
By comparing the initial rates from two experiments where only the concentration of A changes while B remains constant, we see a clear relationship between the change in concentration of A and the change in the reaction rate. Doubling the concentration of A doubles the reaction rate, indicating that A is first order in the reaction. This means the rate of the reaction is directly proportional to the concentration of A.
Examples & Analogies
Imagine you're at a concert and you start talking louder to be heard over the crowd. If there are more people (higher concentration of A), and you talk louder (double your voice), everyone can hear you twice as well (the rate of the sound reaching others doubles).
Determining Order with Respect to [B]
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Chapter Content
To determine the order with respect to [B]:
- Compare Experiment 1 and Experiment 3. Here, the initial concentration of A is kept constant (0.10 mol dm$^{-3}), while the initial concentration of B doubles (from 0.10 to 0.20 mol dm$^{-3}).
- Observe the change in initial rate: The rate quadruples (from 2.0 x 10$^{-3}$ to 8.0 x 10$^{-3}$ mol dm$^{-3} s^{-1}$). Since doubling [B] results in a quadrupling of the rate (2^n = 4), the reaction is second order (n=2) with respect to B.
Detailed Explanation
In this instance, by analyzing the initial rates from two experiments where only the concentration of B changes, we can see that doubling the concentration of B has a more pronounced effect on the reaction rate than doubling A did. The rate quadrupling indicates that B is second order when considering its concentration; the rate is proportional to the square of the change in concentration of B.
Examples & Analogies
Consider turning up the volume on two speakers in a room. If you increase the volume on one speaker (B) and it suddenly becomes four times louder, itβs like saying that the effect of that speaker grows quadratically with the volume you adjustβsmall changes make a huge difference.
Writing the Rate Expression
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Chapter Content
The complete rate expression for this reaction is: Rate = k [A]$^{1}$ [B]$^{2}$, which is commonly written as Rate = k [A] [B]$^{2}$.
Detailed Explanation
The rate expression combines our findings about the orders of reaction with respect to the reactants A and B. It shows how the rate of the reaction depends on the concentrations of A and B, with their respective orders given as exponents. Since we determined that A is first order (m=1) and B is second order (n=2), the final rate expression captures the relationship between concentration and rate effectively.
Examples & Analogies
Think of the rate expression like a recipe where each ingredient contributes differently to the flavor of a dish. A first-order ingredient (A) is like adding a basic seasoning that changes the taste linear to how much you add, while a second-order ingredient (B) is like a special spice that magnifies the flavor more significantlyβits effect grows quadratically as you add more.
Calculating the Rate Constant
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Chapter Content
To calculate the value and units of the rate constant (k): Use Experiment 1: 2.0 x 10$^{-3}$ mol dm$^{-3}$ s$^{-1}$ = k * (0.10 mol dm$^{-3}) * (0.10 mol dm$^{-3})$^2. Thus, 2.0 x 10$^{-3}$ = k * (0.0010), leading to k = 2.0 mol$^{-2}$ dm$^{6}$ s$^{-1}$.
Detailed Explanation
Using the data from one of our experiments and substituting the values into our rate expression allows us to solve for the rate constant k. This constant quantifies the relationship between the concentration of reactants and the rate of the reaction. Here, the units of k tell us how to relate the different concentrations and the reaction rate to each other.
Examples & Analogies
Calculating k is akin to finding the price-per-unit measure for a bulk purchase. For instance, if you buy flour in bulk, the total cost relates to how much flour you buy. Here, k represents how much the concentration of our ingredients (reactants) affects the overall cost (reaction rate) of our dish (reaction).
Key Concepts
-
Rate Expression: Shows the mathematical relationship between reaction rate and reactant concentration.
-
Reaction Order: Indicates how the rate depends on the concentration of each reactant.
-
Rate Constant (k): A constant proportional to the rate of reaction, specific to conditions.
Examples & Applications
In the reaction A + B β Products, doubling the concentration of A results in doubling the reaction rate. This implies that the reaction is first order with respect to A.
In the same reaction, if doubling B leads to a quadrupling of the rate, this indicates that the reaction is second order with respect to B.
Memory Aids
Interactive tools to help you remember key concepts
Rhymes
For rates, just compare, analyze, don't despair; order found, k defined, chemistryβs a fair!
Stories
Once upon a time, in the world of reactions, A met B at a party. They danced (collided) to find products. Their order was known by comparing their dance moves (rates) β more collisions, better dance, and higher order!
Memory Tools
CRA for Rate: Compare, Rate, Analyze.
Acronyms
OAR (Order, Analyze, Rate) for remembering how to determine the order of a reaction.
Flash Cards
Glossary
- Rate Expression
A mathematical representation that relates the rate of a reaction to the concentrations of the reactants.
- Reaction Order
An exponent in the rate law equation that indicates the dependence of the reaction rate on the concentration of a reactant.
- Rate Constant (k)
A proportionality constant in the rate expression that links the speed of a reaction to the concentrations of the reactants.
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