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1 Dr. Laurence Lavelle Kinetics: The Differential and Integrated Rate Laws in Chemistry (and Physics, Biology, etc.) In general, for all reactions: aA β†’ bB + cC Rate = βˆ’ 1 [] = 1 [] = 1 [] *Notice for the reactants, there is a negative sign in front. This is because as time progresses, the concentration of reactant decreases. For products, their concentration over time increases which is why theirs is positive (no negative sign in front). As reactant A goes to product B: A β†’ B Rate = βˆ’ 1 [] = [] *In the following derivations of the three integrated rate laws, we assume the stoichiometric coefficient "a" in front of reactant A is 1. 1 st order reaction Differential Rate Law = βˆ’[] = [] Separate the variables [] [] = βˆ’ Integrate both sides of the equation ∫ [] [] = ∫ βˆ’ = βˆ’ ∫ Indefinite integral constant, b ln[]= βˆ’ + At time t = 0, = ln[] 0 where [A]0 is the initial reactant concentration Integrated Rate Law (linear form) []= βˆ’ + [] To more clearly see the exponential relationship between time, t, and reactant concentration, [A], for a first-order reaction we can convert the integrated first-order rate-law (linear form) to its non-linear exponential form:

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Page 1: Kinetics: The Differential and Integrated Rate Laws …...1 Dr. Laurence Lavelle Kinetics: The Differential and Integrated Rate Laws in Chemistry (and Physics, Biology, etc.) In general,

1

Dr. Laurence Lavelle

Kinetics: The Differential and Integrated Rate Laws in Chemistry (and Physics, Biology, etc.)

In general, for all reactions: aA β†’ bB + cC

Rate = βˆ’1π‘Žπ‘Žπ‘‘π‘‘[𝐴𝐴]𝑑𝑑𝑑𝑑

= 1𝑏𝑏𝑑𝑑[𝐡𝐡]𝑑𝑑𝑑𝑑

= 1𝑐𝑐𝑑𝑑[𝐢𝐢]𝑑𝑑𝑑𝑑

*Notice for the reactants, there is a negative sign in front. This is because as time progresses, the concentration of reactant decreases. For products, their concentration over time increases which is why theirs is positive (no negative sign in front).

As reactant A goes to product B: A β†’ B

Rate = βˆ’1π‘Žπ‘Žπ‘‘π‘‘[𝐴𝐴]𝑑𝑑𝑑𝑑

= π‘˜π‘˜[𝐴𝐴]𝑛𝑛

*In the following derivations of the three integrated rate laws, we assume the stoichiometric coefficient "a" in front of reactant A is 1.

1st order reaction Differential Rate Law 𝐑𝐑𝐑𝐑𝐑𝐑𝐑𝐑 = βˆ’π’…π’…[𝑨𝑨]

𝒅𝒅𝒅𝒅= π’Œπ’Œ[𝑨𝑨]𝟏𝟏

Separate the variables 𝑑𝑑[𝐴𝐴][𝐴𝐴]

= βˆ’π‘˜π‘˜ 𝑑𝑑𝑑𝑑

Integrate both sides of the equation ∫ 𝑑𝑑[𝐴𝐴][𝐴𝐴]

= βˆ«βˆ’π‘˜π‘˜ 𝑑𝑑𝑑𝑑 = βˆ’π‘˜π‘˜ βˆ«π‘‘π‘‘π‘‘π‘‘

Indefinite integral constant, b ln[𝐴𝐴] = βˆ’π‘˜π‘˜π‘‘π‘‘ + 𝑏𝑏

At time t = 0, 𝑏𝑏 = ln[𝐴𝐴]0 where [A]0 is the initial reactant concentration

Integrated Rate Law (linear form) π₯π₯π₯π₯[𝑨𝑨] = βˆ’π’Œπ’Œπ’…π’… + π₯π₯π₯π₯[𝑨𝑨]𝟎𝟎

To more clearly see the exponential relationship between time, t, and reactant concentration, [A], for a first-order reaction we can convert the integrated first-order rate-law (linear form) to its non-linear exponential form:

Page 2: Kinetics: The Differential and Integrated Rate Laws …...1 Dr. Laurence Lavelle Kinetics: The Differential and Integrated Rate Laws in Chemistry (and Physics, Biology, etc.) In general,

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Integrated Rate Law (linear form) ln [𝐴𝐴] = βˆ’π‘˜π‘˜π‘‘π‘‘ + ln[𝐴𝐴]0

Raise both sides to the power of e 𝑒𝑒ln [𝐴𝐴] = π‘’π‘’βˆ’π‘˜π‘˜π‘˜π‘˜ 𝑒𝑒ln [𝐴𝐴]0

Simplify, and obtain non-linear form [𝐴𝐴] = [𝐴𝐴]0 π‘’π‘’βˆ’π‘˜π‘˜π‘˜π‘˜

One can also then write the non-linear differential rate law:

Rate = βˆ’π‘‘π‘‘[𝐴𝐴]π‘‘π‘‘π‘˜π‘˜

= π‘˜π‘˜[𝐴𝐴] = π‘˜π‘˜[𝐴𝐴]0 π‘’π‘’βˆ’π‘˜π‘˜π‘˜π‘˜

2nd order reaction

Differential Rate Law 𝐑𝐑𝐑𝐑𝐑𝐑𝐑𝐑 = βˆ’π’…π’…[𝑨𝑨]𝒅𝒅𝒅𝒅

= π’Œπ’Œ[𝑨𝑨]𝟐𝟐

Separate the variables βˆ’π‘‘π‘‘[𝐴𝐴][𝐴𝐴]2

= π‘˜π‘˜ 𝑑𝑑𝑑𝑑

Integrate both sides of the equation βˆ«βˆ’ 𝑑𝑑[𝐴𝐴][𝐴𝐴]2

= βˆ«π‘˜π‘˜ 𝑑𝑑𝑑𝑑 = π‘˜π‘˜ βˆ«π‘‘π‘‘π‘‘π‘‘

Indefinite integral constant, b βˆ’οΏ½βˆ’ 1[𝐴𝐴]οΏ½ = π‘˜π‘˜π‘‘π‘‘ + 𝑏𝑏

At time t = 0, 𝑏𝑏 = οΏ½ 1[𝐴𝐴]0

οΏ½ where [A]0 is the initial reactant concentration

Integrated Rate Law 𝟏𝟏[𝑨𝑨]

= π’Œπ’Œπ’…π’… + 𝟏𝟏[𝑨𝑨]𝟎𝟎

Zero-order reaction

Differential Rate Law 𝐑𝐑𝐑𝐑𝐑𝐑𝐑𝐑 = βˆ’π’…π’…[𝑨𝑨]

𝒅𝒅𝒅𝒅= π’Œπ’Œ[𝑨𝑨]𝟎𝟎

Simplify βˆ’π‘‘π‘‘[𝐴𝐴]π‘‘π‘‘π‘˜π‘˜

= π‘˜π‘˜

Separate the variables 𝑑𝑑[𝐴𝐴] = βˆ’π‘˜π‘˜π‘‘π‘‘π‘‘π‘‘

Integrate both sides of the equation βˆ«π‘‘π‘‘[𝐴𝐴] = βˆ«βˆ’π‘˜π‘˜ 𝑑𝑑𝑑𝑑 = βˆ’π‘˜π‘˜ βˆ«π‘‘π‘‘π‘‘π‘‘

Indefinite integral constant, b [𝐴𝐴] = βˆ’π‘˜π‘˜π‘‘π‘‘ + 𝑏𝑏

At time t = 0, 𝑏𝑏 = [𝐴𝐴]0 where [A]0 is the initial reactant concentration

Integrated Rate Law [𝑨𝑨] = βˆ’π’Œπ’Œπ’…π’… + [𝑨𝑨]𝟎𝟎

Page 3: Kinetics: The Differential and Integrated Rate Laws …...1 Dr. Laurence Lavelle Kinetics: The Differential and Integrated Rate Laws in Chemistry (and Physics, Biology, etc.) In general,

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First, Second, and Zero Order Plots for Chemical Reactions

1st order reaction

ln [𝐴𝐴] = βˆ’π‘˜π‘˜π‘‘π‘‘ + ln[A]0

2nd order reaction

1[𝐴𝐴]

= π‘˜π‘˜π‘‘π‘‘ + 1

[𝐴𝐴]0

Zero-order reaction

[𝐴𝐴] = βˆ’π‘˜π‘˜π‘‘π‘‘ + [𝐴𝐴]0

Page 4: Kinetics: The Differential and Integrated Rate Laws …...1 Dr. Laurence Lavelle Kinetics: The Differential and Integrated Rate Laws in Chemistry (and Physics, Biology, etc.) In general,

4

Integrated Rate Law (continued)

- As reactant A goes to product B: aA β†’ bB

Rate = βˆ’1π‘Žπ‘Žπ‘‘π‘‘[𝐴𝐴]𝑑𝑑𝑑𝑑

= π‘˜π‘˜[𝐴𝐴]𝑛𝑛

*In the following derivations of the three integrated rate laws, we assume the stoichiometric coefficient "a" in front of reactant A is no longer 1.

β€’ Therefore, with each new integrated rate law, the proportionality constant is now written as ak'. However, when a rate constant is given, we treat it as a generic proportionality constant and call it k. This is because when an experiment is first performed in lab, the overall balanced reaction with correct coefficients is unknown. To figure out the order of the reaction, the data points are plotted and the slope is calculated and just called k.

1st order reaction: 2A β†’ B Differential Rate Law Rate = βˆ’1

2𝑑𝑑[𝐴𝐴]π‘‘π‘‘π‘˜π‘˜

= π‘˜π‘˜[𝐴𝐴]1

Separate the variables 𝑑𝑑[𝐴𝐴][𝐴𝐴]

= βˆ’2π‘˜π‘˜ 𝑑𝑑𝑑𝑑

Integrate both sides of the equation ∫ 𝑑𝑑[𝐴𝐴][𝐴𝐴]

= βˆ«βˆ’2π‘˜π‘˜ 𝑑𝑑𝑑𝑑 = βˆ’2π‘˜π‘˜ βˆ«π‘‘π‘‘π‘‘π‘‘

Indefinite integral constant, b ln[𝐴𝐴] = βˆ’2π‘˜π‘˜π‘‘π‘‘ + 𝑏𝑏

At time t = 0, 𝑏𝑏 = 𝑙𝑙𝑙𝑙[𝐴𝐴]0 where [A]0 is the initial reactant concentration

Integrated Rate Law (linear form) ln [𝐴𝐴] = βˆ’2π‘˜π‘˜β€²π‘‘π‘‘ + ln[A]0

Page 5: Kinetics: The Differential and Integrated Rate Laws …...1 Dr. Laurence Lavelle Kinetics: The Differential and Integrated Rate Laws in Chemistry (and Physics, Biology, etc.) In general,

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2nd order reaction: 3A β†’ B

Differential Rate Law Rate = βˆ’13𝑑𝑑[𝐴𝐴]π‘‘π‘‘π‘˜π‘˜

= π‘˜π‘˜[𝐴𝐴]2

Separate the variables 𝑑𝑑[𝐴𝐴][𝐴𝐴]2

= βˆ’3π‘˜π‘˜ 𝑑𝑑𝑑𝑑

Integrate both sides of the equation βˆ«βˆ’ 𝑑𝑑[𝐴𝐴][𝐴𝐴]2

= ∫3π‘˜π‘˜ 𝑑𝑑𝑑𝑑 = 3π‘˜π‘˜ βˆ«π‘‘π‘‘π‘‘π‘‘

Indefinite integral constant, b βˆ’οΏ½βˆ’ 1[𝐴𝐴]οΏ½ = 3π‘˜π‘˜π‘‘π‘‘ + 𝑏𝑏

At time t = 0, 𝑏𝑏 = οΏ½ 1[𝐴𝐴]0

οΏ½ where [A]0 is the initial reactant concentration

Integrated Rate Law 1[𝐴𝐴]

= 3π‘˜π‘˜β€²π‘‘π‘‘ + 1[𝐴𝐴]0

Zero-order reaction: 4A β†’ B

Differential Rate Law Rate = βˆ’14𝑑𝑑[𝐴𝐴]π‘‘π‘‘π‘˜π‘˜

= π‘˜π‘˜[𝐴𝐴]0

Simplify βˆ’14𝑑𝑑[𝐴𝐴]π‘‘π‘‘π‘˜π‘˜

= π‘˜π‘˜

Separate the variables 𝑑𝑑[𝐴𝐴] = βˆ’4π‘˜π‘˜π‘‘π‘‘

Integrate both sides of the equation βˆ«π‘‘π‘‘[𝐴𝐴] = βˆ«βˆ’4π‘˜π‘˜ 𝑑𝑑𝑑𝑑 = βˆ’4π‘˜π‘˜ βˆ«π‘‘π‘‘π‘‘π‘‘

Indefinite integral constant, b [𝐴𝐴] = βˆ’4π‘˜π‘˜π‘‘π‘‘ + 𝑏𝑏

At time t = 0, 𝑏𝑏 = [𝐴𝐴]0 where [A]0 is the initial reactant concentration

Integrated Rate Law [𝐴𝐴] = βˆ’4π‘˜π‘˜β€²π‘‘π‘‘ + [𝐴𝐴]0

Page 6: Kinetics: The Differential and Integrated Rate Laws …...1 Dr. Laurence Lavelle Kinetics: The Differential and Integrated Rate Laws in Chemistry (and Physics, Biology, etc.) In general,

6

Half-Life

- The half-life of a reaction (t1/2) is defined as the time it takes for the concentration of the reactant to decrease to half its original concentration.

-The shorter the half-life, the faster the reaction...the faster the reaction, the larger the rate constant.

1st order reaction

Integrated Rate Law 𝑙𝑙𝑙𝑙[𝐴𝐴] = βˆ’π‘˜π‘˜π‘‘π‘‘ + 𝑙𝑙𝑙𝑙[𝐴𝐴]0

At time t = t1/2 [𝐴𝐴] = 12

[𝐴𝐴]0

Substitute for [A] ln 12

[𝐴𝐴]0 = βˆ’π‘˜π‘˜π‘‘π‘‘1 2⁄ + ln[𝐴𝐴]0

Rearrange the terms ln 12

[𝐴𝐴]0 βˆ’ ln[𝐴𝐴]0 = βˆ’π‘˜π‘˜π‘‘π‘‘1 2⁄

ln 12

[𝐴𝐴]0[𝐴𝐴]0

= βˆ’π‘˜π‘˜π‘‘π‘‘1 2⁄

βˆ’0.693 = βˆ’π‘˜π‘˜π‘‘π‘‘1 2⁄

Half-life equation π’…π’…πŸπŸ πŸπŸβ„ = 𝟎𝟎.πŸ”πŸ”πŸ”πŸ”πŸ”πŸ”π’Œπ’Œ

Page 7: Kinetics: The Differential and Integrated Rate Laws …...1 Dr. Laurence Lavelle Kinetics: The Differential and Integrated Rate Laws in Chemistry (and Physics, Biology, etc.) In general,

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2nd order reaction

Integrated Rate Law 1[𝐴𝐴] = π‘˜π‘˜π‘‘π‘‘ + 1

[𝐴𝐴]0

At time t = t1/2 [𝐴𝐴] = 12

[𝐴𝐴]0 Therefore 1[𝐴𝐴]

= 2 βˆ™ 1[𝐴𝐴]0

Substitute for [A] 2 βˆ™ 1[𝐴𝐴]0

= π‘˜π‘˜π‘‘π‘‘1 2⁄ + 1[𝐴𝐴]0

Rearrange the terms 2 βˆ™ 1[𝐴𝐴]0

βˆ’ 1[𝐴𝐴]0

= π‘˜π‘˜π‘‘π‘‘1 2⁄

1[𝐴𝐴]0

= π‘˜π‘˜π‘‘π‘‘1 2⁄

Half-life equation π’…π’…πŸπŸ πŸπŸβ„ = πŸπŸπ’Œπ’Œ[𝑨𝑨]𝟎𝟎

*Note that the half-life for a 2nd order reaction depends on the initial concentration of reactant; it is inversely proportional. Thus, the larger the initial concentration, the smaller the half-life.

Zero-order reaction

Integrated Rate Law [𝐴𝐴] = βˆ’π‘˜π‘˜π‘‘π‘‘ + [𝐴𝐴]0

At time t = t1/2 [𝐴𝐴] = 12

[𝐴𝐴]0

Substitute for [A] 12

[𝐴𝐴]0 = βˆ’π‘˜π‘˜π‘‘π‘‘1 2⁄ + [𝐴𝐴]0

Rearrange the terms π‘˜π‘˜π‘‘π‘‘1 2⁄ = [𝐴𝐴]0 βˆ’12

[𝐴𝐴]0

π‘˜π‘˜π‘‘π‘‘1 2⁄ = 12

[𝐴𝐴]0

Half-life equation π’…π’…πŸπŸ πŸπŸβ„ = [𝑨𝑨]πŸŽπŸŽπŸπŸπ’Œπ’Œ

*Note that the half-life for a zero-order reaction depends on the initial concentration of reactant; it is directly proportional. Thus, the larger the initial concentration, the larger the half-life.

Page 8: Kinetics: The Differential and Integrated Rate Laws …...1 Dr. Laurence Lavelle Kinetics: The Differential and Integrated Rate Laws in Chemistry (and Physics, Biology, etc.) In general,

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Examples Using Integrated Rate Laws and

Half-Lives in Chemistry

1st order reaction

2N2O5(g) β†’ 4NO2(g) + O2(g)

β€’ Write the overall rate expression for this first order reaction.

𝒓𝒓𝒓𝒓𝒅𝒅𝒓𝒓 = π’Œπ’Œ[π‘΅π‘΅πŸπŸπ‘Άπ‘ΆπŸ“πŸ“]𝟏𝟏

*Note that the exponent does not match the coefficient in front of N2O5. By just looking at the overall balanced equation, you cannot tell the order of the reaction.

β€’ The half-life of N2O5 at 25˚C is 1.87 x 104 seconds. Determine the rate constant for the above reaction.

t1 2⁄ = 0.693

k

1.87 Γ— 104 = 0.693

k

π’Œπ’Œ = πŸ”πŸ”.πŸ•πŸ• Γ— πŸπŸπŸŽπŸŽβˆ’πŸ“πŸ“ π¬π¬βˆ’πŸπŸ

β€’ Using the information above, if you were to start with 0.250 M N2O5, how much is left after 10.0 hours?

𝑙𝑙𝑙𝑙[𝐴𝐴] = βˆ’π‘˜π‘˜π‘‘π‘‘ + 𝑙𝑙𝑙𝑙[𝐴𝐴]0

𝑙𝑙𝑙𝑙[𝐴𝐴] = βˆ’(3.7 Γ— 10βˆ’5 sβˆ’1)(3.6 Γ— 104s) + ln[0.250]

[𝑨𝑨] = 𝟎𝟎.πŸŽπŸŽπŸ”πŸ”πŸ”πŸ”πŸŽπŸŽ 𝐌𝐌

Page 9: Kinetics: The Differential and Integrated Rate Laws …...1 Dr. Laurence Lavelle Kinetics: The Differential and Integrated Rate Laws in Chemistry (and Physics, Biology, etc.) In general,

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1st order reaction

2N2O(g) β†’ 2NO(g) + O2(g)

β€’ Write the overall rate expression for this first order reaction.

𝒓𝒓𝒓𝒓𝒅𝒅𝒓𝒓 = π’Œπ’Œ[π‘΅π‘΅πŸπŸπ‘Άπ‘Ά]𝟏𝟏

*Note that the exponent does not match the coefficient in front of N2O. By just looking at the overall balanced equation, you cannot tell the order of the reaction.

β€’ The half-life of N2O at 1000 K is 0.912 seconds. Determine the rate constant for the above reaction.

t1 2⁄ = 0.693

k

0.912 = 0.693

k

π’Œπ’Œ = 𝟎𝟎.πŸ•πŸ•πŸ”πŸ” π¬π¬βˆ’πŸπŸ

β€’ Using the information above, if you were to start with 1.50 M N2O5, how much is left after 20 seconds?

𝑙𝑙𝑙𝑙[𝐴𝐴] = βˆ’π‘˜π‘˜π‘‘π‘‘ + 𝑙𝑙𝑙𝑙[𝐴𝐴]0

𝑙𝑙𝑙𝑙[𝐴𝐴] = βˆ’(0.76 sβˆ’1)(20 s) + ln[1.50]

[𝑨𝑨] = πŸ”πŸ”.πŸ•πŸ•πŸ”πŸ” Γ— πŸπŸπŸŽπŸŽβˆ’πŸ•πŸ• 𝐌𝐌

β€’ Using the equation 𝑙𝑙𝑙𝑙[𝐴𝐴] = βˆ’2π‘˜π‘˜β€²π‘‘π‘‘ + 𝑙𝑙𝑙𝑙[𝐴𝐴]0 and the information above, calculate k’.

π‘˜π‘˜ = 2π‘˜π‘˜β€²

0.76 sβˆ’1 = 2π‘˜π‘˜β€²

𝟎𝟎.πŸ”πŸ”πŸ‘πŸ‘ π¬π¬βˆ’πŸπŸ = π’Œπ’Œβ€²

Page 10: Kinetics: The Differential and Integrated Rate Laws …...1 Dr. Laurence Lavelle Kinetics: The Differential and Integrated Rate Laws in Chemistry (and Physics, Biology, etc.) In general,

10

2nd order reaction

2C4H6(g) β†’ C8H12(g)

β€’ Write the overall rate expression given that the experimentally determined reaction of the dimerization of butadiene is second order.

𝒓𝒓𝒓𝒓𝒅𝒅𝒓𝒓 = π’Œπ’Œ[π‘ͺπ‘ͺπŸ’πŸ’π‘―π‘―πŸ”πŸ”]𝟐𝟐

*Note that in this example the exponent does match the coefficient in front of C4H6. However, this is just a coincidence. By just looking at the overall balanced equation, you cannot tell the order of the reaction.

β€’ The dimerization reaction of butadiene is second order and has a rate

constant of 0.0140M-1·s-1 at 500˚C. Determine the C4H6 concentration after 115.0 seconds if the initial concentration of C4H6 is 0.0500 M.

1[𝐴𝐴] = π‘˜π‘˜π‘‘π‘‘ +

1[𝐴𝐴]0

1[𝐴𝐴] = (0.0140 Mβˆ’1 Β· sβˆ’1 )(115.0 s) +

1[0.0500]

1[𝐴𝐴] = 21.6

[𝑨𝑨] = 𝟎𝟎.πŸŽπŸŽπŸ’πŸ’πŸ”πŸ”πŸ”πŸ” 𝐌𝐌

β€’ Using the information above, calculate the half-life for the dimerization reaction of butadiene when the initial concentration of C4H6 is 0.0500M.

𝑑𝑑1 2⁄ = 1

π‘˜π‘˜[𝐴𝐴]0

𝑑𝑑1 2⁄ =1

(0.0140Mβˆ’1. sβˆ’1)[0.0500]

π’…π’…πŸπŸ πŸπŸβ„ = πŸπŸπŸ’πŸ’πŸ”πŸ”πŸŽπŸŽ 𝐬𝐬

Page 11: Kinetics: The Differential and Integrated Rate Laws …...1 Dr. Laurence Lavelle Kinetics: The Differential and Integrated Rate Laws in Chemistry (and Physics, Biology, etc.) In general,

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2nd order reaction

2HI(g) β†’ H2(g) + I2(g)

β€’ Write the overall rate expression for this experimentally determined second order reaction.

𝒓𝒓𝒓𝒓𝒅𝒅𝒓𝒓 = π’Œπ’Œ[𝑯𝑯𝑯𝑯]𝟐𝟐

β€’ This second order reaction has a rate constant of 6.4 x 10-9 M-1Β·s-1 at 500 K. Determine the concentration of HI after 90 days if the initial concentration of C4H6 is 0.850 M.

1[𝐴𝐴] = π‘˜π‘˜π‘‘π‘‘ + 1[𝐴𝐴]0

1[𝐴𝐴] = (6.4 Γ— 10βˆ’9 Mβˆ’1 Β· sβˆ’1 )(7776000 s) + 1[0.850]

1[𝐴𝐴] = 1.23

[𝑨𝑨] = 𝟎𝟎.πŸ‘πŸ‘πŸπŸπŸ”πŸ” 𝐌𝐌

β€’ Using the information above, calculate the half-life for the decomposition of HI when the initial concentration of HI is 2.00 M

𝑑𝑑1 2⁄ = 1π‘˜π‘˜[𝐴𝐴]0

𝑑𝑑1 2⁄ =1

(6.4 Γ— 10βˆ’9 Mβˆ’1 Β· sβˆ’1)[2.00]

π’…π’…πŸπŸ πŸπŸβ„ = πŸ•πŸ•.πŸ‘πŸ‘ Γ— πŸπŸπŸŽπŸŽπŸ•πŸ• 𝐬𝐬

β€’ Using the equation 1[𝐴𝐴] = 2π‘˜π‘˜β€²π‘‘π‘‘ + 1[𝐴𝐴]0

and the information above,

calculate k’ and discuss whether this reaction is kinetically favorable.

π‘˜π‘˜ = 2π‘˜π‘˜β€²

6.4 Γ— 10βˆ’9 Mβˆ’1 Β· sβˆ’1 = 2π‘˜π‘˜β€²

πŸ”πŸ”.𝟐𝟐 Γ— πŸπŸπŸŽπŸŽβˆ’πŸ”πŸ” πŒπŒβˆ’πŸπŸ Β· π¬π¬βˆ’πŸπŸ = π’Œπ’Œβ€²

This reaction is kinetically unfavorable and will take a long time to occur as the rate constant is ~10-9: the smaller the rate constant, the slower the reaction.

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Zero-order reaction

2NH3(g) β†’ N2(g) + 3H2(g)

β€’ The above reaction, known as the reverse Haber Bosh process takes place on a hot platinum surface. Write the overall rate expression for this zero order reaction.

𝒓𝒓𝒓𝒓𝒅𝒅𝒓𝒓 = π’Œπ’Œ[π‘΅π‘΅π‘―π‘―πŸ”πŸ”]𝟎𝟎

*Note that the exponent does not match the coefficient in front of NH3. By just looking at the overall balanced equation, you cannot tell that this is a zero order reaction.

β€’ At a given temperature, the rate constant for the decomposition of

ammonia is 5.63 x 10-4 MΒ·s-1. Determine the initial concentration of NH3, if after 90.0 seconds the remaining concentration was 0.599 M.

[𝐴𝐴] = βˆ’π‘˜π‘˜π‘‘π‘‘ + [𝐴𝐴]0

[0.599] = βˆ’(5.63 Γ— 10βˆ’4M βˆ™ sβˆ’1)(90.0s) + [𝐴𝐴]0

[𝑨𝑨]𝟎𝟎 = 𝟎𝟎.πŸ”πŸ”πŸ“πŸ“πŸŽπŸŽ 𝐌𝐌

β€’ Using the information above, calculate the half-life for the decomposition of ammonia in the reverse Haber Bosh process if the initial concentration of ammonia was 0.350 M.

𝑑𝑑1 2⁄ = [𝐴𝐴]02π‘˜π‘˜

𝑑𝑑1 2⁄ = 0.350 M

2(5.63 Γ— 10βˆ’4M βˆ™ sβˆ’1)

π’…π’…πŸπŸ πŸπŸβ„ = πŸ”πŸ”πŸπŸπŸπŸ 𝐬𝐬

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Radioactive Decay

- In microbiology and physics labs, we frequently solve problems about carbon dating and radioactive decay. Radioactive decay is a first order reaction. In these types of problems, the rate constant k is referred to as the decay constant, and N is the number of radioactive nuclei.

Differential Rate Law 𝑹𝑹𝒓𝒓𝒅𝒅𝒓𝒓 = βˆ’π’…π’…π‘΅π‘΅π’…π’…π’…π’…

= π’Œπ’Œπ‘΅π‘΅

Separate the variables 𝑑𝑑𝑑𝑑𝑑𝑑

= βˆ’π‘˜π‘˜ 𝑑𝑑𝑑𝑑

Integrate both sides of the equation ∫ 𝑑𝑑𝑑𝑑𝑑𝑑

= βˆ«βˆ’π‘˜π‘˜ 𝑑𝑑𝑑𝑑 = βˆ’π‘˜π‘˜ βˆ«π‘‘π‘‘π‘‘π‘‘

Indefinite integral constant, b ln𝑁𝑁 = βˆ’π‘˜π‘˜π‘‘π‘‘ + 𝑏𝑏

At time t = 0, 𝑏𝑏 = ln 𝑁𝑁0 where N0 is the initial number of radioactive nuclei.

Integrated Rate Law (linear form) π₯π₯π₯π₯ 𝑡𝑡 = βˆ’π’Œπ’Œπ’…π’… + π₯π₯π₯π₯π‘΅π‘΅πŸŽπŸŽ

To more clearly see the exponential relationship between time, t, and the number of radioactive nuclei, N, we can convert the integrated first-order rate-law (linear form) to its non-linear exponential form:

Raise both sides to the power of e 𝑒𝑒ln 𝑑𝑑 = π‘’π‘’βˆ’π‘˜π‘˜π‘˜π‘˜ 𝑒𝑒ln 𝑑𝑑0

Simplify, and obtain non-linear form 𝑁𝑁 = 𝑁𝑁0 π‘’π‘’βˆ’π‘˜π‘˜π‘˜π‘˜

One can also then write the non-linear differential rate law: π‘…π‘…π‘Žπ‘Žπ‘‘π‘‘π‘’π‘’ = βˆ’π‘‘π‘‘π‘‘π‘‘

π‘‘π‘‘π‘˜π‘˜= π‘˜π‘˜π‘π‘ = π‘˜π‘˜[𝑁𝑁]0 π‘’π‘’βˆ’π‘˜π‘˜π‘˜π‘˜

β€’ Carbon-14 dating is used to determine the age of various objects and has a half-life of 5730 years. If a sample today contains 0.096 mg of 14C, how much 14C was present in this sample 12,530 years ago? Hint: To simplify, let mass of 14C = number of radioactive nuclei, N

t1 2⁄ = 0.693k

= 5730 years

π‘˜π‘˜ = 1.21 Γ— 10βˆ’4 π‘¦π‘¦π‘’π‘’π‘Žπ‘Žπ‘¦π‘¦βˆ’1

𝑙𝑙𝑙𝑙 𝑁𝑁 = βˆ’π‘˜π‘˜π‘‘π‘‘ + 𝑙𝑙𝑙𝑙 𝑁𝑁0

𝑙𝑙𝑙𝑙(0.096 mg) = βˆ’(1.21 Γ— 10βˆ’4 π‘¦π‘¦π‘’π‘’π‘Žπ‘Žπ‘¦π‘¦βˆ’1)(12530 π‘¦π‘¦π‘’π‘’π‘Žπ‘Žπ‘¦π‘¦) + 𝑙𝑙𝑙𝑙 𝑁𝑁0

π‘΅π‘΅πŸŽπŸŽ = 𝟎𝟎.πŸ’πŸ’πŸ”πŸ”πŸ•πŸ• 𝐦𝐦𝐦𝐦

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Population Growth: Bacteria

- In biology labs, we study bacteria growth under various conditions. Population growth is mathematically equivalent to a first order reaction, but the slope is positive because we are modelling population growth. In these types of problems, the rate constant k is referred to as the growth constant, and N is the number of bacteria and some time, t.

Integrated Rate Law π₯π₯π₯π₯ 𝑡𝑡 = π’Œπ’Œπ’…π’… + π₯π₯π₯π₯π‘΅π‘΅πŸŽπŸŽ

Raise both sides to the power of e 𝑒𝑒ln 𝑑𝑑 = π‘’π‘’π‘˜π‘˜π‘˜π‘˜ 𝑒𝑒ln 𝑑𝑑0

Simplify to get exponential form 𝑡𝑡 = π‘΅π‘΅πŸŽπŸŽ π’“π’“π’Œπ’Œπ’…π’…

β€’ Suppose the initial number of bacteria in your culture dish is 1.40 million. You check back in an hour and the number of bacteria has increased to 10.35 million. What is the growth rate of this bacterial species (per min)?

One can use the linear or exponential equation above where the initial number of bacteria is No and the number of bacteria after an hour is N.

𝑁𝑁 = 𝑁𝑁0 π‘’π‘’π‘˜π‘˜π‘˜π‘˜

[10.35] = [1.40]π‘’π‘’π‘˜π‘˜(60 π‘šπ‘šπ‘šπ‘šπ‘›π‘›)

7.39 = 𝑒𝑒(60 π‘šπ‘šπ‘šπ‘šπ‘›π‘›)π‘˜π‘˜

ln(7.39) = 𝑙𝑙𝑙𝑙 𝑒𝑒60π‘˜π‘˜

2.00 = 60π‘˜π‘˜

π’Œπ’Œ = 𝟎𝟎.πŸŽπŸŽπŸ”πŸ”πŸ”πŸ” π’Žπ’Žπ’Žπ’Žπ’Žπ’Žβˆ’πŸπŸ

= πŸ”πŸ”.πŸ”πŸ”% π’Žπ’Žπ’Žπ’Žπ’Žπ’Žβˆ’πŸπŸ

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Drug Concentration

- In biology labs, we study the effectiveness of the body to metabolize certain administered drugs. The body's metabolism of drugs can be defined as a first order reaction. In these types of problems, the rate constant k is characterized as the removal rate of the drug through metabolism or excretion, and C is the concentration of the substance in the body.

Integrated Rate Law π₯π₯π₯π₯ [π‘ͺπ‘ͺ] = βˆ’π’Œπ’Œπ’…π’… + π₯π₯π₯π₯[𝐂𝐂]𝟎𝟎

Raise both sides to the power of e 𝑒𝑒ln [𝐢𝐢] = π‘’π‘’βˆ’π‘˜π‘˜π‘˜π‘˜ 𝑒𝑒ln [𝐢𝐢]0

Simplify to get exponential form [π‘ͺπ‘ͺ] = [π‘ͺπ‘ͺ]𝟎𝟎 π’“π’“βˆ’π’Œπ’Œπ’…π’…

β€’ Patients diagnosed with depression have a decreased concentration of serotonin in their brain. To help increase this concentration, doctors administer Selective Serotonin Reuptake Inhibitors (SSRIs) to the patients. Normal levels of serotonin in a healthy individual range from 101-283 ng/ml. Serotonin is metabolized by the body at a rate of 9.63 x 10-6 s-1. Assume that when the SSRI is administered, the serotonin concentration increases to 175.0 ng/ml. How long will it take for the serotonin concentration to fall below 100.0 ng/ml?

[𝐢𝐢] = [𝐢𝐢]0π‘’π‘’βˆ’π‘˜π‘˜π‘˜π‘˜

[100.0] = [175.0]π‘’π‘’βˆ’(9.63 Γ— 10βˆ’6 π‘ π‘ βˆ’1)π‘˜π‘˜

0.571 = π‘’π‘’βˆ’(9.63 Γ— 10βˆ’6 π‘ π‘ βˆ’1)π‘˜π‘˜

ln 0.571 = 𝑙𝑙𝑙𝑙 π‘’π‘’βˆ’(9.63 Γ— 10βˆ’6 π‘ π‘ βˆ’1)π‘˜π‘˜

βˆ’0.560 = βˆ’9.63 Γ— 10βˆ’6 𝑑𝑑

𝒅𝒅 = πŸ“πŸ“.πŸ‘πŸ‘πŸπŸ Γ— πŸπŸπŸŽπŸŽπŸ’πŸ’ 𝒔𝒔


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